Treatment of release layer and inkjet ink formulations

ABSTRACT

Aqueous inkjet ink formulations comprising a solvent including water and a co-solvent, a water soluble or water dispersible polymeric resin and a colorant, and a method for facilitating the use of such an aqueous inkjet ink in an indirect printing system in which the ink is jetted onto a hydrophobic release layer of an intermediate transfer member before having the solvent removed therefrom and being transferred to a substrate, wherein prior to the jetting of the ink the release layer is brought into contact with an aqueous solution of a positively charged polymeric chemical agent. Other aspects are also described.

The present application claims the benefit of U.S. Ser. No. 15/182,539,filed 14 Jun. 2016, which is a continuation-in-part of U.S. Ser. No.12/382,930, filed Sep. 4, 2014 as the national phase ofPCT/IB2013/000757, filed Mar. 5, 2013, which claims Paris Conventionpriority from, and the benefit under U.S. law of, provisionalapplications Nos. 61/641,258 (filed 1 May 2012), 61/611,557 (filed 15Mar. 2012), 61/607,537 (filed 6 Mar. 2012), and 61/606,913 (filed 5 Mar.2012). U.S. Ser. No. 15/182,539 is also a continuation-in-part of U.S.Ser. No. 14/382881, filed Sep. 4, 2014 as the national phase ofPCT/IB2013/051755, which was filed Mar. 5, 2013, and claims ParisConvention priority from, and the benefit under U.S. law of, USprovisional applications Nos. 61/641,653 (filed 2 May 2012 and titled,“Inkjet Ink Film Constructions”, 61/641,223 (filed 1 May 2012 and titled“Inkjet Ink Compositions”), 61/619,372 (filed 2 Apr. 2012 and titled“Inkjet Ink Compositions”), 61/611,570 (filed 15 Mar. 2012 and titled“Inkjet Ink Compositions”), 61/606,985 (filed 5 Mar. 2012 and titled“Inkjet Ink Film Constructions”) and 61/606,913 (filed Mar. 5. 2012),The contents of all of the aforementioned applications are incorporatedherein by reference.

FIELD AND BACKGROUND

The present invention relates to indirect printing systems, and moreparticularly, to compositions suitable for the treatment of intermediatetransfer members, and to ink formulations suitable for such indirectprinting systems.

Digital printing techniques have been developed that allow a printer toreceive instructions directly from a computer without the need toprepare printing plates. Amongst these are color laser printers that usethe xerographic process. Color laser printers using dry toners aresuitable for certain applications, but they do not produce images of aphotographic quality acceptable for publications, such as magazines.

A process that is better suited for short run high quality digitalprinting is used in the HP-Indigo printer. In this process, anelectrostatic image is produced on an electrically charged image bearingcylinder by exposure to laser light. The electrostatic charge attractsoil-based inks to form a color ink image on the image bearing cylinder.The ink image is then transferred by way of a blanket cylinder ontopaper or any other substrate.

Inkjet and bubble jet processes are commonly used in home and officeprinters. In these processes droplets of ink are sprayed onto a finalsubstrate in an image pattern. In general, the resolution of suchprocesses is limited due to wicking by the inks into paper substrates.Fibrous substrates, such as paper, generally require specific coatingsengineered to absorb the liquid ink in a controlled fashion or toprevent its penetration below the surface of the substrate. Usingspecially coated substrates is, however, a costly option that isunsuitable for certain printing applications, especially for commercialprinting. Furthermore, the use of coated substrates creates its ownproblems in that the surface of the substrate remains wet and additionalcostly and time consuming steps are needed to dry the ink, so that it isnot later smeared as the substrate is being handled, for example stackedor wound into a roll. Furthermore, excessive wetting of the substrate bythe ink causes cockling and makes printing on both sides of thesubstrate (also termed perfecting or duplex printing) difficult, if notimpossible.

Furthermore, inkjet printing directly onto porous paper, or otherfibrous material, results in poor image quality because of variation ofthe distance between the print head and the surface of the substrate.

Using an indirect or offset printing technique overcomes many problemsassociated with inkjet printing directly onto the substrate. It allowsthe distance between the surface of the intermediate image transfermember and the inkjet print head to be maintained constant and reduceswetting of the substrate, as the ink can be dried on the intermediateimage member before being applied to the substrate. Consequently, thefinal image quality on the substrate is less affected by the physicalproperties of the substrate.

The use of transfer members which receive ink droplets from an ink orbubble jet apparatus to form an ink image and transfer the image to afinal substrate have been reported in the patent literature. Variousones of these systems utilize inks having aqueous carriers, non-aqueouscarrier liquids or inks that have no carrier liquid at all (solid inks).

The use of aqueous based inks has a number of distinct advantages.Compared to non-aqueous based liquid inks, the carrier liquid is nottoxic and there is no problem in dealing with the liquid that isevaporated as the image dries. As compared with solid inks, the amountof material that remains on the printed image can be controlled,allowing for thinner printed images and more vivid colors.

Generally, a substantial proportion or even all of the liquid isevaporated from the image on the intermediate transfer member, beforethe image is transferred to the final substrate in order to avoidbleeding of the image into the structure of the final substrate. Variousmethods are described in the literature for removing the liquid,including heating the image and a combination of coagulation of theimage particles on the transfer member, followed by removal of theliquid by heating, air knife or other means.

Generally, silicone coated transfer members are preferred, since thisfacilitates transfer of the dried image to the final substrate. However,silicone is hydrophobic which causes the ink droplets to bead on thetransfer member. This makes it more difficult to remove the water in theink and also results in a small contact area between the droplet and theblanket that renders the ink image unstable during rapid movement of thetransfer member.

Surfactants and salts have been used to reduce the surface tension ofthe droplets of ink so that they do not bead as much. While these dohelp to alleviate the problem partially, they do not solve it. Hence,compositions suitable for the treatment of the intermediate transfermember of an indirect printing system are desired.

BRIEF DESCRIPTION

The presently claimed invention pertains to particular aspects of anovel printing process and system for indirect digital inkjet printingusing aqueous inks, other aspects of which are described and claimed inother applications of the same Applicant which were filed atapproximately the same time as the present application. Further detailson examples of such printing systems are provided in co-pending PCTapplication Nos. PCT/IB2013/051716 (Agent's reference LIP 5/001 PCT),published as WO 2013/132418; PCT/IB2013/051717 (Agent's reference LIP5/003 PCT), published as WO 2013/132419; and PCT/IB 2013/051718 (Agent'sreference LIP 5/006 PCT), published as WO 2013/132420. A non-limitativedescription of such printing systems will be provided below.

Briefly, the printing process shared in particular, but not exclusively,by the above-mentioned systems, comprises directing droplets of anaqueous inkjet ink onto an intermediate transfer member having ahydrophobic release layer to form an ink image on the release layer, theink including an organic polymeric resin and a coloring agent in anaqueous carrier, and the transfer member having a hydrophobic outersurface. Upon impinging upon the intermediate transfer member, each inkdroplet in the ink image spreads to form an ink film. The ink is thendried while the ink image is being transported by the intermediatetransfer member, by evaporating the aqueous carrier from the ink imageto leave a residue film of resin and coloring agent. The residue film isthen transferred to a substrate. Without wishing to be bound by theory,it is presently believed that mutually attractive intermolecular forcesbetween molecules in the outer region of each ink droplet nearest thesurface of the intermediate transfer member and molecules on the surfaceof the intermediate transfer member itself (e.g. between negativelycharged molecules in the ink and positively charged molecules on thesurface of the intermediate transfer member) counteract the tendency ofthe ink film produced by each droplet to bead under the action of thesurface tension of the aqueous carrier, without causing each droplet tospread by wetting the surface of the intermediate transfer member. Oneaspect of the presently claimed invention pertains to a method oftreating the surface of the intermediate transfer member to enable itssufficient interaction with the molecules of the ink, including chemicalagents suitable for use in such a method, as well as printed articlesobtainable by the use of said method and agents.

In accordance with an embodiment of the present invention, in a printingprocess such as that just described or as will described in more detailhereinbelow, in which an aqueous inkjet ink containing a negativelycharged polymeric resin is jetted onto a hydrophobic release layer priorto being transferred to a substrate, there is provided a method fortreating the release layer prior to the jetting of the aqueous ink ontothe release layer, the method comprising contacting the release layerwith an aqueous solution or dispersion of a polymeric chemical agenthaving at least one of (1) a positive charge density of at least 3 meq/gof chemical agent and an average molecular weight of at least 250, and(2) a nitrogen content of at least 1% and a molecular weight of at least10,000. In some embodiments, the chemical agent, which may alternativelybe referred to as a conditioning or pre-treatment agent, has a positivecharge density of at least 3 meq/g and the average molecular weight isat least 5,000. In some embodiments, the chemical agent has a positivecharge density of at least 6 meq/g and the average molecular weight isat least 1,000. In some embodiments, the chemical agent has a nitrogencontent of at least 1 wt. % and an average molecular weight of at least50,000. In some embodiments, the chemical agent has a nitrogen contentof at least 18 wt. % and an average molecular weight of at least 10,000.

In some embodiments, the positive charge density is at least 0.5 meq/g,at least 1 meq/g, at least 2 meq/g, at least 3 meq/g, at least 4 meq/g,at least 5 meq/g, 6 meq/g, at least 7 meq/g, at least 8 meq/g, at least9 meq/g, at least 10 meq/g, at least 11 meq/g, at least 12 meq/g, atleast 13 meq/g, at least 14 meq/g, at least 15 meq/g, at least 16 meq/g,at least 17 meq/g, at least 18 meq/g, at least 19 meq/g, or at least 20meq/g of chemical agent.

In some embodiments, the chemical agent has an average molecular weightof at least 500, at least 800, at least 1,000, at least 1,300, at least1,700, at least 2,000, at least 2,500, at least 3,000, at least 3,500,at least 4.000, at least 4,500, at least 5,000, at least 10,000, atleast 15,000, at least 20,000, at least 25,000, at least 50,000, atleast 100,000, at least 150,000, at least 200,000, at least 250,000, atleast 500,000, at least 750,000, at least 1,000.000, or at least2,000,000.

In some embodiments, the chemical agent comprises one or more positivelychargeable nitrogen atoms. (By a “positively chargeable polymer” or“positively chargeable group” is meant a polymer or chemical moietywhich either can readily add a proton (e.g. —NH₂) or has a permanentpositive charge (e.g. —N(CH₃)₃′); as used herein, the term refers to aninherent property of the polymer or moiety, and thus may encompasspolymers or moieties which are in an environment in which such protonsare added, as well as polymers in an environment in which such protonsare not added. In contrast, the term “a positively charged” polymer orgroup refers to a polymer or group in an environment in which one ormore such protons have been added or which has a permanent positivecharge.) In some embodiments, the one or more chargeable nitrogen atomsof the chemical agent are selected from the group of primary, secondaryand tertiary amines and quaternary ammonium groups and combinations ofsuch groups. In some embodiments, such groups are covalently bound to apolymeric backbone and/or constitute part of such a backbone. In someembodiments the one or more nitrogen atoms are part of a. cyclic moiety.In some embodiments, the one or more nitrogen atoms constitute at least1%, at least 1.4%, at least 2%, at least 5%, at least 8%, at least 10%,at least 15%, at least 18%, at least 20%, at least 24%, at least 30%, atleast 35%, at least 40%, at least 45%, or at least 50% by weight of thechemical agent.

In some embodiments, the chemical agent is a solid at room temperature.

In some embodiments, the chemical agent is selected from the groupconsisting of linear polyethylene imine, branched polyethylene imine,modified polyethylene imine, poly(diallyldimethylammonium chloride),poly(4-vinylpyridine), polyallylamine, a vinylpyrrolidone-dimethylaminopropyl methacrylamide co-polymer (Viviprint131), a vinyl caprolactam-dimethylaminopropyl methacryamide hydroxyethylmethacrylate copolymer (Viviprint 200), a quatemized copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate with diethyl sulfate(Viviprint 650), a guar hydroxypropyltrimonium chloride, and ahydroxypropyl guar hydroxypropyltrimonium chloride. In sonicembodiments, the chemical agent is a polyethylene imine.

In some embodiments, the chemical agent is stable at temperatures of upto at least 100° C., at least 125° C., or at least 150° C. In thiscontext, “stable” means that decomposition is not observed usingthermogravimetric analysis (TGA).

In some embodiments, the concentration of the chemical agent in thesolution or dispersion prior to application is not more than 5 wt. %,not more than 4 wt. %, not more than 3 wt.%, not more than 2 wt. %, notmore than I wt. %, not more than 0.5 wt. %, not more than 0.4 wt. %, notmore than 0.3 wt. %, not more than 0.2 wt. %, not more than 0.1 wt. %,not more than 0.05 wt. %, or not more than 0.01 wt. %.

In some embodiments, the chemical agent is applied to the release layerusing a roller. In some embodiments, the chemical agent is applied byspraying. In some embodiments, the chemical agent is applied to therelease layer by spraying and then evened using a metering roller. Insome embodiments, the metering roller is chrome-plated. In someembodiments, the chemical agent is applied to the release layer so thatthe thickness of the solution or dispersion of chemical agent on therelease layer prior to removal of the solvent is less than 1,000microns, less than 900 microns, less than 800 microns, less than 700microns, less than 600 microns, less than 500 microns, less than 400microns, less than 300 microns, less than 200 microns, less than 100microns, less than 50 microns, less than 10 microns, or less than 1micron.

In some embodiments, the method further comprises removing (e.g.evaporating) the solvent in which the chemical agent is dissolved ordispersed. In some embodiments, the average thickness of the chemicalagent on the release layer after evaporation of the solvent is not morethan 1,000 nm, not more than 900 nm, not more than 800 nm, not more than700 nm, not more than 600 nm, not more than 500 nm, not more than 400nm, not more than 300 nm, not more than 200 mu, not more than 100 inn,not more than 90 nm, not more than 80 nm, not more than 70 nm, not morethan 60 nm, not more than 50 nm, not more than 40 nm, not more than 30nm, not more than 20 nm, not more than 15 nm, not more than 10 nm, notmore than 9 nm, not more than 8 nm, not more than 7 nm, not more than 6nm, not more than 5 nm, not more than 4 nm, not more than 3 nm, not morethan 2 nm, or not more than 1 nm.

In some embodiments, the concentration of the chemical agent on therelease layer after evaporation of the solvent is not more than 50 mgper square meter, not more than 40 mg/m², not more than 30 mg/m², notmore than 20 mg/m², not more than 10 mg/m², not more than 5 mg/m², notmore than 4 m/m², not more than 3 mg/m², not more than 2 mg/m², not morethan 1 mg/m², not more than 0.5 mg/m², not more than 0.1 mg/m², not morethan 0.05 mg/m² or not more than 0.01 mg/m².

In some embodiments, the hydrophobic outer release layer comprises asilane, silyl or silanol-modified or -terminated polydialkylsiloxanesilicone polymer, or hybrids of such polymers. In some embodiments,these silicone polymers are cross-linked by condensation curing of thesilane groups. Thus, in some embodiments, the release layer comprises across-linked silanol- or silyl-terminated. polydialkylsiloxane. In someembodiments, the hydrophobic outer release layer comprisessilanol-terminated polydialkylsiloxane cross-linked with apolyethylsilicate oligomer.

In some embodiments, the temperature of the release layer when contactedwith the aqueous solution or dispersion of the chemical agent is atleast 60° C., at least 80° C., at least 100° C., at least 110° C., atleast 120° C., at least 130° C., at least 140° C. or at least 150° C.

In some embodiments, the change in the contact angle of a drop ofdistilled water on the release layer to which the chemical agent hasbeen applied and the solvent removed. therefrom is not more than 10degrees, not more than 9 degrees, not more than 8 degrees, not more than7 degrees, not more than 6 degrees, not more than 5 degrees, not morethan 4 degrees, not more than 3 degrees, not more than 2 degrees, notmore than 1 degree relative to a drop of distilled water on the releaselayer to which the chemical agent has not been applied. In someembodiments, the change is at least 0.1 degrees, at least 0.2 degrees,at least 0.3 degrees, at least 0.4 degrees, at least 0.5 degrees, atleast 0.6 degrees, at least 0.7 degrees, at least 0.8 degrees, at least0.9 degrees or at least 1 degree relative to a drop of distilled wateron the release layer to which the chemical agent has not been applied.

In some embodiments, the reduction in the contact angle of a drop ofdistilled water on the release layer to which the chemical agent hasbeen applied and the solvent removed therefrom is not more than 20%, notmore than 15%, not more than 10%, not more than 9%, more than 8%, notmore than 7%, not more than 6%, not more than 5%, not more than 4%, notmore than 3%, not more than 2%, or not more than 1% relative to thecontact angle of a drop of distilled water on the release layer to whichthe chemical agent has not been applied. In some embodiments, thereduction in the contact angle is at least 0.1%, at least 0.2%, at least0.3%, at least 0.4%, at least 0.5%, at least 0.6%, at least 0.7%, atleast 0.8%, at least 0.9%, or at least 1% relative to the contact angleof a drop of distilled water on the release layer to which the chemicalagent has not been applied. In some embodiments, the contact angle onthe release layer to which the chemical agent has been applied and thesolvent removed therefrom is at least 90 degrees,

In some embodiments, the method further comprises printing an ink dropto form an ink film on the chemical agent on the release layer, whereinthe ratio of charges in the ink film to the charges in the chemicalagent in the region covered by said ink film is at least 1:1, at least2:1, at least 3:1, at least 4:1, at least 5:1, at least 10:1, at least20:1, at least 30:1, at least 40:1, at least 50:1, at least 60:1, atleast 70:1 or at least 80:1.

In some embodiments, the method fw:ther comprises printing an aqueousinkjet ink image on the release layer having the chemical agentthereupon; the aqueous inkjet ink comprising an aqueous solvent, acolorant, preferably a pigment, and a negatively chargeable polymericresin; removing the solvent from the printed aqueous inkjet ink; andtransferring the image to a substrate.

In some embodiments, when the substrate is Condat Gloss® 135 gsm coatedpaper, the optical density of the printed image on the substrate is atleast 50% greater than the optical density of the same image whenprinted under identical conditions but without application of thechemical agent to the release layer. In some embodiments, the opticaldensity is at least 60% greater. In some embodiments, the opticaldensity is at least 70% greater. In some embodiments, the opticaldensity is at least 80% greater. In some embodiments, the opticaldensity is at least 90% greater. In some embodiments, the opticaldensity is at least 100% greater, or at least 150% greater, or at least200% greater or at least 250% greater, or at least 300% greater, or atleast 350% greater, or at least 400% greater, or at least 450% greater,or at least 500% greater.

There is also provided, in accordance with an embodiment of theinvention, a hydrophobic release layer of an intermediate transfermember of a printing system, the hydrophobic release layer havingdisposed thereupon a polymeric chemical agent having (1) a nitrogencontent of at least 1 wt. % and at least one of (a) a positive chargedensity of at least 3 meq/g of chemical agent and an average molecularweight of at least 5,000 (b) a positive charge density of 6 meq/g ofchemical agent and an average molecular weight of at least 1,000, and(c) an average molecular weight of at least 50,000, and/or (2) anitrogen content of at least 18 wt. % and an average molecular weight ofat least 10,000.

In some embodiments, the polymer disposed on the release layer containsone or more chargeable nitrogen atoms.

In some embodiments, the thickness of the chemical agent disposed on therelease layer is not more than 1,000 nm, not more than 900 nm, not morethan 800 nm, not more than 700 nm, not more than 600 nm, not more than500 nm, not more than 400 nm, not more than 300 nm, not more than 200nm, not more than 100 nm, not more than 90 nm, not more than 80 nm, notmore than 70 nm, not more than 60 nm, not more than 50 nm not more than40 nm, not more than 30 nm, not more than 20 tun, not more than 10 nm,not more than 9 nm, not more than 8 nm, not more than 7 nm, not morethan 6 nm, not more than 5 tun, not more than 4 nm, not more than 3 nm,not more than 2 nm, or not more than 1 nm.

In some embodiments, the chemical agent disposed upon the release layerhas an average molecular weight of at least 800, at least L000, at least1,300, at least 1,700, at least 2,000, at least 2,500, at least 3,000,at least 3,500, at least 4,000, at least 4,500, at least 5,000, of atleast 10,000, at least 15,000, at least 20,000, at least 25,000, atleast 50,000, at least 100,000, at least 150,000, at least 200,000, atleast 250,000, at least 500,000, at least 750,000, at least 1,000,000,or at least 2,000,000.

In some embodiments, the positive charge density of the chemical agentdisposed upon the release layer is at least 0.5 meq/g, at least 1 meq/g,at least 2 meq/g, at least 3 meq/g, at least 4 meq/g, at least 5 meq/g,at least 6 meq/g, at least 7 meq/g, at least 8 meq/g, at least 9 meq/g,at least 10 meq/g, at least 11 meq/g, at least 12 meq/g, at least 13meq/g, at least 14 meq/g, at least 15 meq/g, at least 16 meq/g, at least17 meq/g, at least 18 meq/g, at least 19 meq/g, or at least 20 meq/g ofchemical agent.

In some embodiments, the chemical agent disposed upon the release layeris selected from the group consisting of linear polyethylene minim,branched polyethylene imine, modified polyethylene imine,poly(diallyldimethylammonium chloride), poly(4-vinylpyridine),polyallylamine, a vinyl pyrrolidone-dimethylaminopropyl methacrylamideco-polymer (Viviprint 131), a vinyl caprolactam-ditneklaminopropylmethacryamide hydroxyethyl methacrylate copolymer (Viviprint 200), aquaternized copolymer of vinyl pyrrolidone and ditnethylaminoethylmethacrylate with diethyl sulfate (Viviprint 650), a guarhydroxypropyltrimonium chloride, and a hydroxypropyl guarhydroxypropyl-trimonium chloride. In some embodiments, the chemicalagent is polyethylene imine.

In some embodiments, the concentration of the chemical agent disposed onthe release layer is not more than 50 mg per square meter, not more than40 mg/m², not more than 30 mg/m², not more than 20 mg/m², not more than10 mg/m², not more than 5 mg/m², not more than 4 mg/m², not more than 3mg/m², not more than 2 mg/m², not more than 1 mg/m², or not more than0.5 mg/m².

There is also provided, in accordance with an embodiment of theinvention, a printed ink image on a substrate, the printed ink imagecomprising a water-soluble or water-dispersible polymeric resin, whereinat least one of the following is true: (a) the image has an X-RayPhotoelectron Spectroscopy (XPS) peak at 402.0±0.4 eV, 402.0±0.3 eV, or402.0±0.2 eV; (b) the image has been printed by a printing method inaccordance with an embodiment of the invention in which a chemical agentas described herein is applied to a hydrophobic release layer of anintermediate transfer member; (c) the image has on its outer surfacedistal to the substrate a polymeric chemical agent containing at least 1wt. % of one or more chargeable nitrogen atoms and having at least oneof (1) a positive charge density of at least 3 meq/g of chemical agentand an average molecular weight of at least 250 and (2) a molecularweight of at least 10,000; (e) the ratio of the surface concentration ofnitrogen at the outer surface of the image distal to the substrate tothe bulk concentration of nitrogen within the image is at least 1.2:1,at least 1.3:1, at least 1.5:1, at least 1,75:1, at least 2:1, at least3:1, or at least 5: Lratio being at least 1,2:1, at least 1.3:1, atleast 1.5:1, at least 1.75:1, at least 2:1, at least 3:1, or at least5:1; (1) the atomic surface concentration ratio of nitrogen to carbon(N/C) at the image surface distal to the substrate to the atomic bulkconcentration ratio of nitrogen to carbon (N/C) at the depth, is atleast 1.1:1, at least 1.2:1, at least 1.3:1, at least 1.5:1, at least1.75:1, or at least 2:1; (g) the surface concentration of secondaryamines, tertiary amines, and/or an ammonium group at the image surfacedistal to the substrate exceeds their respective bulk concentrations ata depth of at least 30 nanometers below the surface. In someembodiments, the chemical agent on the printed ink image contains one ormore chargeable nitrogen atoms.

In some embodiments, the chemical agent on the printed ink image has anaverage molecular weight of at least 800, at least 1,000, at least1,300, at least 1,700, at least 2,000, at least 2,500, at least 3,000,at least 3,500, at least 4,000, at least 4,500, at least 5,000, of atleast 10,000, at least 15,000, at least 20,000, at least 25,000, atleast 50,000, at least 100,000, at least 150,000, at least 200,000, atleast 250,000, at least 500,000, at least 750,000, at least 1,000,000,or at least 2,000,000.

In some embodiments, the positive charge density of the chemical agenton the printed image is at least 0.5 meq/g, at least 1 meq/g, at least 2meq/g, at least 3 meq/g, at least 4 meq/g, at least 5 meq/g, 6 meq/g, atleast 7 meq/g, at least 8 meq/g, at least 9 meq/g, at least 10 meq/g, atleast 11 meq/g, at least 12 meq/g, at least 13 meq/g, at least 14 meq/g,at least 15 meq/g, at least 16 meq/g, at least 17 meq/g, at least 18meq/g, at least 19 meq/g, or at least 20 meq/g of chemical agent.

In some embodiments the polymer on the printed image is selected fromthe group consisting of linear polyethylene imine, branched polyethyleneimine, modified polyethylene imine, poly(diallyidimethylammoniumchloride), poly(4-vinylpyridine), polyallylamine, a vinylpyrrolidone-dimethylaminopropyl methacrylamide co-polymer (Viviprint131), a vinyl caprolactam-dimethylaminopropyl methacryamide hydroxyethylmethacrylate copolymer (Viviprint 200), a quaternized copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate with diethyl sulfate(Viviprint 650), a guar hydroxypropyltrimonium chloride, and ahydroxypropyl guar hydroxypropyltrimonium chloride. In some embodimentsthe polymer in the printed image is polyethylene imine.

In some embodiments, a surface concentration of nitrogen at the surfacedistal to the substrate on which the printed ink image rests exceeds abulk concentration of nitrogen within the bulk of the ink image, thebulk concentration being measured at a depth of at least 30 nanometers,at least 50 nanometers, at least 100 nanometers, at least 200nanometers, or at least 300 nanometers below the ink image surfacedistal to the substrate, and the ratio of the surface concentration tothe bulk concentration is at least 1.1 to 1. In some embodiments, thebulk concentration is measured at a depth of at least 30 nm from the inkimage surface distal to the substrate.

There is also provided, in accordance with an embodiment of theinvention, a water-based inkjet ink formulation comprising: (a) asolvent containing water and, optionally, a co-solvent, said waterconstituting at least 8 wt. % of the formulation; (b) at least onecolorant dispersed or at least partly dissolved within the solvent, thecolorant constituting at least 1 wt. % of the formulation; and (c) anorganic polymeric resin, which is dispersed or at least partiallydissolved within the solvent, the resin constituting 6 to 40 wt. % ofthe formulation, wherein the average molecular weight of the resin is atleast 8,000, the ink formulation having at least one of (i) a viscosityof 2 to 25 centipoise (cP) at at least one temperature in the range of20-60° C. and (ii) a surface tension of not more than 50 milliNewton/m(mN/m) at at least one temperature in the range of 20-60° C. and whereinat least one of the following two statements is true: (1) the ink issuch that, when substantially dried, (a) at at least one temperature inthe range of 90° C. to 195° C., the dried ink has a first dynamicviscosity in the range of 1,000,000 (1×10⁶) cP to 300,000,000 (3×10⁸)cP, and (b) at at least one temperature in the range of 50° C. to 85°C., the dried ink has a second dynamic viscosity of at least 80,000,000(8×10⁷) cP, wherein the second dynamic viscosity exceeds the firstdynamic viscosity; and (2) the weight ratio of the resin to the colorantis at least 1:1.

In some embodiments, the ink is such that, when substantially dried, (a)at at least one temperature in the range of 90° C. to 195° C., the driedink has a first dynamic viscosity in the range of 1,000,000 (1×10⁶) cPto 300,000,000 (3×10⁸) cP, and (b) at at least one temperature in therange of 50° C. to 85° C., the dried ink has a second dynamic viscosityof at least 80,000,000 (8×10⁷) cP, wherein the second dynamic viscosityexceeds the first dynamic viscosity. In some embodiments, the firstdynamic viscosity is at most 25·10⁷ cP, at most 20·10⁷ cP, at most15·1.0⁷ cP, at most 12·10⁷ cP, at most 10·10⁷ cP, at most 9·10⁷ cP, atmost 8·10⁷ cP, or at most 7·10⁷ cP. In some embodiments, the firstdynamic viscosity is at least 2×10⁶ cP, at least 4×10⁶ cP, at least5×10⁶ cP, at least 6·10⁶ cP, at least 7×10⁶ cP, at least 8×10⁶ cP, atleast 9×10⁶ cP, at least 1×10⁷ cP, at least 1.1×10⁷ cP, at least 1.2·10⁷cP, at least 1.3·10⁷ cP, at least 1.4·10⁷ cP, at least 1.5×10⁷ cP, atleast 1.6×10⁷ cP, at least 2.5×10⁷ cP, or at least 4×10⁷ cP. In someembodiments, the first dynamic viscosity is within a range of 10⁶ cP to2.5·10⁸ cP, 10⁶ cP to 2.0·10⁸ cP, 10⁶ cP to 10⁸ cP, 3·10⁶ cP to 10⁸ cP,5·10⁶ cP to 3·10⁸ cP, 5·10⁶ cP to 3·10⁸ cP, 8·10⁶ cP to 3·10⁸ cP, 8·10⁶cP to 10⁸ cP, 10⁷ cP to 3·10⁸ cP, 10⁷ cP to 2·10⁸ cP, 10⁷ cP to 10⁸ cP,2·10⁷ cP to 3·10⁸ cP, 2·10⁷ cP to 2·10⁸ cP, or 2·10⁷ cP to 10⁸ cP.

In some embodiments, when the ink when substantially dried has a firstdynamic viscosity as previously mentioned, at at least one temperaturein the range of 125° C. to 160° C., the first dynamic viscosity of thesubstantially dried ink is in the range of 10⁷ cP to 3×10⁸ cP. In someof these embodiments, the first dynamic viscosity is at least 1.1×10⁷cP, at least 1.2×10⁷ cP, at least 1.3×10⁷ cP, or at least 1.4×1.0⁷ cP;in some of these embodiments the first dynamic viscosity is at most25·10⁷ cP, at most 20·10⁷ cP, at most 15·10⁷ cP, at most 12·10 ⁷ cP, atmost 10·10⁷ cP, at most 9·10⁷ cP, at most 8·10⁷ cP, or at most 7·10⁷ cP;in some of these embodiments, the first dynamic viscosity is within arange of 10⁷ cP to 3·10⁸ cP, 10⁷ cP to 2·10⁸ cP, 10⁷ cP to 10⁸ cP, 2·10⁷cP to 3·10⁸ cP, 2·10⁷ cP to 2·10⁸ cP, or 2·10⁷ cP to 10⁸ cP.

In some embodiments, the formulation further comprises a dispersant. Insome embodiments, the dispersant constitutes not more than 3.5 wt. %,not more than 3 wt. %, not more than 2.5 wt. %, not more than 2 wt. %,not more than 1.5 wt. %, not more than 1 wt. % or not more than 0.5 wt.% of the formulation.

In some embodiments in which the formulation comprises a dispersant and,when substantially dried, has a first dynamic viscosity as mentionedabove, at at least one temperature in the range of 90° C. to 125° C. thefirst dynamic viscosity of the substantially dried ink is in the rangeof 4×10⁷ cP to 2×10⁸ cP. In some of these embodiments the first dynamicviscosity is at least 5×10⁷ cP or 6×10⁷ cP; in some of these embodimentsthe first dynamic viscosity is at most 5˜10⁷ cP or 6˜10⁷ cP; in some ofthese embodiments the dispersant is selected from the group consistingof a high molecular weight aminourethane (Disperbyk® 198), a modifiedpolyacrylate polymer (EFKA® 4560, EIFKA® 4580), or acrylic blockcopolymer made by controlled free radical polymerisation (EFKA® 4585.EFKA® 7702), or an ethoxylated non-ionic fatty alcohol (Lumiten® N-OC30),

In some embodiments in which the inkjet ink formulation whensubstantially dried has a second dynamic viscosity as mentioned above,the second dynamic viscosity is at least 9·10⁷ cP, at least 10⁸ cP, atleast 1.1·10⁸ cP, at least 1.2·10⁸ cP, at least 1.3·10⁸ cP, at least1.4·10⁸ cP, at least 1.5·10⁸ cP, at least 2.0·10⁸ cP, at least 2.5·10⁸cP, at least 3.0·10⁸ cP, at least 3.5·10⁸ cP, at least 4.0·10⁸ cP, atleast 5.0·10⁸ cP, at least 6·10⁸ cP, at least 7.5·10⁸ cP, at least 10⁹cP, at least 2·10⁹ cP, at least 4·10⁹ cP, or at least 6·10⁹ cP.

In some embodiments in which the inkjet ink formulation whensubstantially dried has a first dynamic viscosity and a second dynamicviscosity as mentioned above, the ratio of the first dynamic viscosityto the second dynamic viscosity is at least 12:1, at least 1.3:1, atleast 1,5:1, at least 1,7:1, at least 2:1, at least 2.5:1, at least 3:1,at least 3.5:1, at least 4:1, at least 4.5:1, at least 5:1, at least6:1, at least 7:1, at least 8:1, at least 10:1, at least 15:1, at least20:1, at least 25:1, at least 50:1, at least 100:1, at least 500:1, orat least 1000:1. In some embodiments, a ratio of said second dynamicviscosity, at 90° C., to said first dynamic viscosity, at 60° C., is atleast 1.2:1, at least 1.3:1, at least 1.5:1, at least 1.7:1, at least2:1, at least 2.5:1, at least 3:1, at least 4:1, at least 4.5:1, atleast 5:1, at least 6:1, at least 7:1, or at least 8:1. In someembodiments, the ratio of the first dynamic viscosity to the seconddynamic viscosity is at most 30:1, at most 25:1, at most 20:1, at most15:1, at most 12:1, or at most 10:1.

In some embodiments, the weight ratio of the polymeric resin to thecolorant is at least 1:I. In some embodiments, the weight ratio of thepolymeric resin to the colorant is at least 1.25:1, at least 1.5:1, atleast 1,75:1, at least 2:1, at least 2.5:1, at least 3:1, at least3.5:1, at least 4:1, at least 5:1, at least 7:1, or at least 10:1. Insome embodiments, the weight ratio of the polymeric resin to thecolorant is at most 15:1, at most 12:1, at most 10:1, at most 7:1, atmost 5:1, at most 4:1. at most 3:1, at most 2.5:1, at most 2:1, or atmost 1.7:1.

In some embodiments, the inkjet ink formulation, when substantiallydried, has a glass transition temperature (T) of at most 50° C., at most47° C., at most 45° C., at most 44° C. at most 43° C., at most 42° C.,at most 40° C., at most 39° C. at most 37° C., at most 35° C., at most32° C., at most 30° C. or at most 28° C.

In some embodiments, the polymeric resin is an acrylic-based polymerselected from an acrylic polymer and an acrylic-styrene copolymer.

In some embodiments, the inkjet ink formulation comprises a co-solvent.In sonic embodiments, the co-solvent is miscible with the water. In someembodiments the co-solvent is miscible with water at the at least oneparticular temperature in the range of 20° C. to 60° C., whereby thesolvent is a single-phase solvent. In some embodiments, the co-solventis selected to provide the single-phase solvent with a reduced vaporpressure relative to water at the at least one particular temperature inthe range of 20° C. to 60° C. In some embodiments, the co-solvent isselected from the group consisting of ethylene glycol, diethyleneglycol, propylene glycol, glycerol, PEG 400, N-methyl pyrrolidone, andmixtures thereof. In some embodiments, the co-solvent is not awater-soluble polymer. In various embodiments, the co-solvent is not awater-soluble polymer having an average molecular weight greater than1000, greater than 750, or greater than 500. In various embodiments, theco-solvent constitutes at least 5 wt. %, at least 10 wt. %, at least 15wt. %, at least 20 wt. %, at least 25 rt.%, at least 30 wt. %, at least35 wt. %, or at least 40 wt. % of the formulation. In some embodiments,the co-solvent constitutes not more than 40 wt. %, not more than 35 wt.%, not more than 30 wt. %, not more than 25 wt. %, not more than 20 wt.%, not more than 15 wt. %, not more than 10 wt. %, or not more than 5wt. % of the formulation. In some embodiments, the ratio of co-solventto water, on a weight-weight basis, is within the range of 0,2:1 to1.5:1.

In some embodiments, the inkjet ink formulation further comprises asurfactant, in addition to the polymeric resin, colorant, water andoptional co-solvent. In some embodiments, the surfactant is present inan amount of not more than 2 wt. %, not more than 1.5 wt. %, not morethan 1 wt. %, or not more than 0.5 wt. %. In some embodiments, thesurfactant is a non-ionic surfactant. In some embodiments, thesurfactant is an anionic surfactant. In some embodiments, the surfactantis a cationic surfactant.

In some embodiments, the polymeric resin has a T_(g) below 50° C. Invarious embodiments, the polymeric resin has a T_(g) that is at most 48°C., at most 47° C., at most 45° C., at most 40° C., at most 35° C., orat most 30° C.

In some embodiments, the average molecular weight of the polymeric resinis not more than 70,000, not more than 65,000, not more than 60,000, notmore than 55,000, not more than 50,000, not more than 45,000 or not morethan 40,000. In some embodiments, the average molecular weight of thepolymeric resin is at least 10,000, at least 15,000, at least 20,000, atleast 25,000 or at least 30,000.

In some embodiments, the average molecular weight of the polymeric resinis at least 70,000, at least 80,000, at least 100,000, at least 120,000,at least 140,000, at least 160,000, at least 180,000, or at least200,000.

In some embodiments, the colorant comprises a pigment or a mixture ofpigments. In some embodiments, the average particle size (D₅₀) of the atleast one pigment is not more than 120 nm, not more than 110 nm, notmore than 100 nm, not more than 90 nm, not more than 80 nm, not morethan 70 mn, not more than 65 nm. or not more than 60 nm. In someembodiments, the average particle size (D₅₀) of the pigment is at least20 nm, at least 25 nm, at least 30 nm, at least 35 nm, at least 40 mm atleast 45 nm, at least 50 nm, at least 55 nm, at least 60 nm, at least 65nm, or at least 70 nm, In various embodiments, the average particle size(D₅₀) of the pigment is in the range of 20-120 nm, in the range of20-110 nm, in the range of 20-100 nm, in the range of 20-90 nm, in therange of 20-80 mm in the range of 20-70 nm, in the range of 30-120 nm,in the range of 30-110 nm, in the range of 30-100 nm, in the range of30-90 nm, in the range of 30-80 nm, in the range of 30-70 nm, in therange of 35-120 nm, in the range of 35-110 nm, in the range of 35-100nm, in the range of 35-90 tun, in the range of 35-80 nm, in the range of35-70 nm, in the range of 40-120 nm, in the range of 40-110 nm, in therange of 40-100 rim, in the range of 40-90 nm, in the range of 40-80 nm,or in the range of 40-70 nm.

In some embodiments, water constitutes at least 10 wt. %, at least 15wt. %, at least 20 wt. %, at least 25 wt. %, at least 30 wt. %, at least35 wt. %, at least 40 wt. %, at least 45 wt. %, at least 50 wt. %, atleast 55 wt. %, at least 60 wt. %, at least 65 wt. %, at least 70 wt. %,at least 75 wt. %, or at least 80 wt. % of the formulation. In someembodiments, water constitutes not more than 85 wt. %, not more than 80wt. %, not more than 75 wt. %, not more than 70 wt. %, not more than 65wt. %, riot more than 60 wt. %, not more than 55 wt. %, not more than 50wt. %, not more than 45 wt. %, or not more than 40 wt. % of theformulation.

In some embodiments, the polymeric resin is a negatively chargeableresin. In some embodiments, the polymer resin is negatively charged.

In some embodiments, the ink when substantially dried contains at least1.2 wt. %, at least 1.5 wt. %, at least 2 wt. %, at least 3 wt. %, atleast 4 wt. %, at least 6 wt. %, at least 8 wt. %, or at least 10 wt. %of the colorant.

In some embodiments, the ink when substantially dried contains at least5 wt. %, at least 7 wt. %, at least 10 wt. %, at least 15 wt. %, atleast 20 wt. %, at least 30 wt. %, at least 40 wt. %, at least 50 wt. %,at least 60 wt. %, or at least 70 wt. % of the polymeric resin.

In some embodiments, a solubility of the resin in water, at atemperature within a temperature range of 20° C. to 60° C., and at a pHwithin a pH range of 8.5 to 10, is at least 3%, at least 5%, at least8%, at least 12%, at least 18%, or at least 25%, by weight of dissolvedresin to weight of solution.

In some embodiments, the inkjet ink formulation comprises a pH-raisingcompound. In some embodiments, the pH-raising compound constitutes notmore than 2 wt. %, not more than 1.5 wt. %, or not more than 1 wt. % ofthe formulation.

There is also provided, in accordance with an embodiment of theinvention, an inkjet ink concentrate comprising: (a) a solventcontaining water and, optionally, a co-solvent; at least one colorantdispersed or at least partly dissolved within said solvent; and anorganic polymeric resin, which is dispersed or at least partiallydissolved within said solvent, wherein the average molecular weight ofsaid resin is at least 8,000, and (d) optionally, at least one of asurfactant, a dispersant, and a pH raising compound; wherein theconcentrate, when diluted with a solvent comprising water and aco-solvent, yields an aqueous inkjet formulation as described herein. Insome embodiments, the concentrate must be diluted with at least 50%, atleast 100%, at least 150%, at least 200%, at least 250%, at least 300%,least 350% or at least 400% solvent on a weight/weight basis relative tothe concentrate to yield the aqueous inkjet ink formulation. In someembodiments, the co-solvent is selected from the group consisting ofglycerol, propylene glycol, ethylene glycol, diethylene glycol, N-methylpyrrolidone, PEG 400, and mixtures thereof.

In some embodiments the inkjet ink formulation has both a viscosity of 2to 25 cP at at least one temperature in the range of 20-60° C. and asurface tension of not more than 50 (mN/m) at at least one temperaturein the range of 20-60° C.

In various embodiments, the second dynamic viscosity is not more than6×10⁹ cP, not more than 5×10⁹ cP, not more than 4×10⁹ cP, not more than3×10⁹ cP, not more than 2×10⁹ cP, not more than 1×10⁹ cP, not more than9×10⁸ cP, not more than 8×10⁸ cP, not more than 7×10⁸ cP, not more than6×10⁸ cP, not more than 5×10⁸ cP, not more than 4×10⁸ cP, not more than3×10⁸ cP, or not more than 2×10⁸ cP,

In some embodiments, the polymeric resin comprises primarily orexclusively one or more negatively chargeable polymers, such aspolyanionic polymers. By a “negatively chargeable polymer” or “nentivelychargeable polymer resin” is meant a polymer or polymeric resin whichhas at least one proton which can easily be removed to yield a negativecharge; as used herein, the term refers to an inherent property of thepolymer, and thus may encompass polymers which are in an environment inwhich such protons are removed, as well as polymers in an environment inwhich such protons are not removed. In contrast, the term “a negativelycharged polymer resin” refers to a resin in an enviromnent in which oneor more such protons have been removed. Examples of negativelychargeable groups are carboxylic acid groups (—COOH), including acrylicacid groups (—CH₂═CH—COOH) and methacrylic acid groups(—CH₂═C(CH₃)—COOH), and sulfonic acid groups (—SO₃H). Such groups can becovalently bound to polymeric backbones; for example styrene-acryliccopolymer resins have carboxylic acid functional groups which readilylose protons to yield negatively-charged moieties. Many polymerssuitable for use in embodiments of the invention, when dissolved inwater, will be negatively charged; others may require the presence of apH raising compound to be negatively charged. Commonly, polymers willhave many such negatively chargeable groups on a single polymermolecule, and thus are referred to as polyanionic polymers. Examples ofpolyanionic polymers include, for instance, polysulfonates such aspolyvinylsulfonates, poly(styrenesulfonates) such as poly(sodiumstyrenesulfonate) (PSS), sulfonated poly(tetrafluoroethylene),polysulfates such as polyvinylsulfates, polycarhoxylates such as acrylicacid polymers and salts thereof (e.g. ammonium, potassium, sodium), forinstance, those available from BASF and DSM Resins, methacrylic acidpolymers and salts thereof (e.g. EUDRAGIT®, a methacrylic acid and ethylacrylate copolymer), carboxymethylcellulose, carboxymethylamylose andcarboxylic acid derivatives of various other polymers, polyanionicpeptides and proteins such as homopolymers and copolymers of acidicamino acids such as glutamic acid, aspartic acid or combinationsthereof, homopolymers and copolymers of uronic acids such as mannuronicacid, galacturonic acid and guluronic acid, and their salts, alginicacid and its salts, hyaluronic acid and its salts, gelatin, carrageenan,polyphosphates such as phosphoric acid derivatives of various polymers,polyphosphonates such as polyvinylphosphonates, as well as copolymers,salts, derivatives, and combinations of the preceding, among variousothers. In some embodiments, the polymeric resin comprises anacrylic-based polymer, viz. a polymer or copolymer made from acrylicacid or an acrylic acid derivative (e.g. methacrylic acid or an acrylicacid ester), such as polyacrylic acid or an acrylic acid-styrenecopolymer. Nominally, the polymeric resin may be, or include, an acrylicstyrene co-polymer. In some embodiments the polymeric resin comprisesprimarily or exclusively an acrylic-based polymer selected from anacrylic polymer and an acrylic-styrene copolymer. In some embodiments,the polymeric resin comprises an aliphatic polyurethane. In someinstances, the polymeric resin is at least partly water soluble; in someinstances, the polymeric resin is water dispersible, and may he providedas an emulsion or a colloid. Examples of such materials that areavailable commercially that have been found suitable for use inembodiments orf the present invention include Joncryl 142-E, Joncryl637, Joncryl 638, Joncryl 8004, Joncryl HPD 296, Neocryl BT-26, NeocrylBT-100, Neocryl BT-102, and Neocryl BT-9. (Joncryl®® and Neocryl® areregistered trademarks of BASF Corporation and DSM, respectively.)

In various embodiments, taken together the water, co-solvent if present,colorant, and polymeric resin constitute at least 65 wt. %, at least 70wt. %, at least 75 wt. %, at least 80 wt. %, at least 85 wt. %, at least90 wt. % or at least 95 wt. % of the formulation.

In some embodiments, the colorant contains less than 5% dye. In someembodiments, the colorant is substantially free of a dye.

In some embodiments, the colorant comprises a dye. In some embodiments,the colorant contains less than 5% pigment. In some embodiments, thecolorant comprises a dye and is substantially free of pigment.

In various embodiments, the polymeric resin constitutes not more than 20wt. %, not more than 19 wt. %. not more than 18 wt. %, not more than 17wt. %, not more than 16 wt. %, not more than 15 wt. %, not more than 14wt. %, not more than 13 wt. %, not more than 12 wt. %, not more than 11wt. %, not more than 10 wt. %, not more than 9 wt.?, or not more than 8wt. % of the formulation.

In some embodiments, the polymeric resin is at least partially solublein the solvent. In some embodiments, the polymeric resin is partiallysoluble in the solvent at a pH of 8.5-10. In various embodiments, at atleast one temperature in the range of 20-60′ C., the solubility of thepolymeric resin in water is at least 2%, at least 3%, at least 5%, atleast 7.5%, or at least 10% on a resin-to-water weight-weight basis.

In some embodiments, at at least one temperature in the range of 60 to100° C., the polymeric resin has a viscosity of less than 10¹¹ cP, of5×10¹° cP or less, of 10¹⁰ cP or less, of 5×10⁹ cP or less, of 10⁹ cP orless, or of 5×10⁸ cP or less.

In some embodiments, at at least one temperature in the range of 125 to170° C., the polymeric resin has a viscosity of 5×10⁸ cP or less, of 10⁸cP or less, or of 5×10⁷ cP or less.

In some embodiments, the polymeric resin consists predominantly ofacrylic styrene copolymer. In some embodiments, the polymeric resinconsists essentially of acrylic styrene copolymer. In variousembodiments, the weight ratio of the acrylic styrene copolymer to thetotal amount of polymeric resin is at least 0.5, at least 0.6, at least0.7, at least 0.8, at least 0.9, at least 0.95, or substantially 1.

In some embodiments, at a temperature in the range of 20-60° C. theviscosity of the formulation is within a range of 2-25 cP. In someembodiments, the viscosity in this temperature range is at least 2 cP,at least 3 cP, at least 4 cP, at least 5 cP, or at least 6 cP. In someembodiments, the viscosity in this temperature range is not more than 25cP, not more than 22 cP, not more than 20 cP, not more than 18 cP, ornot more than 15 cP.

In various embodiments, the surface tension of the formulation at atleast one particular temperature within a temperature range of 20° C. to60° C. is not more than 50 milliNewtorilm, not more than 45 mN/m, or notmore than 40 mN/m. In various embodiments, the surface tension of theformulation at this temperature is at least 18 mN/m, at least 20 mN/m,or at least 22 mN/m.

In some embodiments, other than the polymeric resin and, if present, thedispersant, the formulation is substantially free of water solublepolymer. In some embodiments, the formulation is substantially free ofsaccharide. In some embodiments, the formulation is substantially freeof wax. In some embodiments, other than a pH-controlling agent, theformulation is substantially free of salt. In some embodiments, otherthan salts having the polymeric resin and/or the dispersant, if present,as one of the ions in the salt, the formulation is substantially free ofsalt. In some ethbodiments, the formulation is substantially free ofprecipitant. In some embodiments, the formulation is substantially freeof a dye insolubilizing agent. In some embodiments, the formulation issubstantially free of a coagulating agent. In various embodiments, theformulation contains less than 5 wt. % inorganic filler particles (suchas silica particulates, titanic particulates and alumina particulates),less than 3 wt. % inorganic filler particles, less than 2 wt. %inorganic filler particles, less than 1 wt. % inorganic fillerparticles, less than 0.5 wt. % inorganic filler particles, or less than0.1 wt. % filler particles. In some embodiments, the formulation issubstantially free of inorganic filler particles. In variousembodiments, the formulation is substantially free of a co-solventhaving a molecular weight of 1000 or higher, having a molecular weightof 750 or higher, or having a molecular weight of 500 or higher. In someembodiments, the co-solvent of which the formulation is substantiallyfree is a polymer having a plurality of hydroxyl groups. In someembodiments, the polymer having a plurality of hydroxyl groups isselected from a polyethylene glycol and a polypropylene glycol. In someembodiments, the formulation is devoid or substantially devoid of oilssuch as mineral oils and vegetable oils (e.g. linseed oil and soyhea.noil), or other oils used in offset ink formulations, and thus containsat most 1%, at most 0.5%, at most 0.1%, or at most 0%, by weight, of oneor more oils, cross-linked fatty acids, or fatty acid derivativesproduced upon air-drying.

In various embodiments, the total amount of material in the formulationwhich remains as solids when the formulation is substantially driedconstitutes less than 20 wt. %, less than 19 wt. %, less than 18 wt. %,less than 17 wt. %, less than 16 wt. %, less than 15 wt. %, less than 14wt. %, less than 13 wt. %, or less than 12 wt. % of the formulation.

In various embodiments, the colorant and the polymeric resin togetherconstitute at least 50 wt. %, at least 55 wt. %, at least 60 wt. %, atleast 65 wt. %, at least 70 wt. %, at least 75 wt. %, at least 80 wt. %,at least 85 wt. %, at least 90 wt. %, at least 95 wt. % or at least 97wt. % of the material in the formulation which remains as solids whenthe formulation is substantially dried.

In accordance with an embodiment of an invention, in a printing processsuch as that described above or as will described in more detailhereinbelow, in which an aqueous inkjet ink containing a negativelychargeable polymeric resin is jetted onto a hydrophobic release layerprior to being transferred to a substrate, there is provided a methodfor treating the release layer prior to the jetting of the aqueous inkonto the release layer, the method comprising contacting the releaselayer with an aqueous solution or dispersion of a positively chargeablepolymeric chemical agent.

DETAILED DESCRIPTION

As mentioned above, aspects of the presently claimed invention pertainto a particular aspect of a novel printing process and apparatus forindirect digital inkjet printing using aqueous inks.

Aspects of the presently claimed invention pertain to aqueous inkjet inkformulations. These formulations may be used in indirect printingsystems having an intermediate transfer member. In particular thepresent formulations may be used as part of and in conjunction with,respectively, a novel printing process and system for indirect digitalinkjet printing, other novel aspects of which have been described andclaimed in other applications of the same applicant which were filed onor about Mar. 5, 2013: PCT/IB2013/000840, published as WO 2013/132345and entitled “INK FILM CONSTRUCTIONS”; PCT/IB2013/051718, published asWO 2013/132420 and entitled “PRINTING SYSTEM”; PCT/IB2013/000822,published as WO 2013/132343 and entitled “INK FILM CONSTRUCTIONS”;PCT/IB2013/051743, published as WO 2013/132432 and entitled“INTERMEDIATE TRANSFER MEMBERS FOR USE WITH INDIRECT PRINTING SYSTEMS”;PCT/IB2013/051727, published as WO 2013/132424 and entitled “CONTROLAPPARATUS AND METHOD FOR A DIGITAL PRINTING SYSTEM”; PCT/IB2013/051751,published as WO 2013/132438 and entitled “PROTONATABLE INTERMEDIATETRANSFER MEMBERS FOR USE WITH INDIRECT PRINTING SYSTEMS”;PCT/IB2013/051716, published as WO 2013/132418 and entitled “DIGITALPRINTING PROCESS”; PCT/IB2013/051717, published as WO 2013/132419 andentitled “DIGITAL PRINTING SYSTEM”; PCT/IB2013/000782, published as WO2013/132340 and entitled “INK FILM CONSTRUCTIONS”; PCT/IB2013/050245,published as WO 2013/132356 and entitled “APPARATUS AND METHODS FORMONITORING OPERATION OF A PRINTING SYSTEM”; and PCTIB/2013/051719,published as WO 2013/136220 and entitled “ENDLESS FLEXIBLE BELT FOR APRINTING SYSTEM”. The contents of these applications are incorporated byreference herein for all purposes, as if fully set forth herein.

Briefly, the printing process comprises directing droplets of an aqueousinkjet ink onto an intermediate transfer member having a hydrophobicrelease layer to form an ink image on the release layer, the inkincluding a negatively charged polymeric resin and a colorant in anaqueous carrier. The term “release layer” is used herein to denote thehydrophobic outer surface of the intermediate transfer member, and whilein some instances that outer surface may be part of a layer that isreadily distinguishable from the rest of the intermediate transfermember, in theory it is possible that the intermediate transfer memberhas a uniform construction, in which case the outer surface will not,strictly speaking, be part of a separate layer. Upon impinging upon theintermediate transfer member, each ink droplet in the ink image spreadsto form an ink film having a pancake-like structure. The ink is thendried while the ink image is on the intermediate transfer member,generally while being transported by the intermediate transfer merriber,by evaporating the aqueous carrier from the ink image to leave a residuefilm of resin and coloring agent. The residue film is then transferredto a substrate.

Upon impinging upon the surface of the intermediate transfer member,each ink droplet tends to spread out into a pancake-like structure dueto the kinetic energy of the droplet itself. However, because the inkused in the process described above is aqueous, but the release layer ofthe intermediate transfer member is hydrophobic, the ink droplets tendto bead on the transfer member. The term “to bead” is used herein todescribe the action of surface tension to cause a pancake or disk-likefilm to contract radially and increase in thickness so as to form abead, that is to say a near-spherical globule. Thus the chemicalcompositions of the ink and of the chemical agent which applied to thesurface of the intermediate transfer member are selected, infer alio, soas to counteract the tendency of the ink film produced by each dropletto bead under the action of the surface tension of the aqueous carrier,without causing each droplet to spread by wetting the surface of theintermediate transfer member. Without wishing to be bound by theory, itis presently believed that, in the case of the presently claimedinvention, this is due to mutually attractive intermolecular forcesbetween molecules in the region of each droplet nearest the surface ofthe intermediate transfer member and molecules on the surface of theintermediate transfer member itself.

In the context of this patent application, “chargeable nitrogen atom”refers to both a nitrogen atom which may be positively charged at acidicpH, such as a primary, secondary or tertiary amine nitrogen atom, whichas is known in the art function as Bronsted bases to abstract a protonfrom a Bronsted acid to form the corresponding ammonium cation, as wellas to a quaternary ammonium ion, which bears a permanent positivecharge. In the context of this patent application, when referring to thechemical agent, “positive charge density of X” means the chemical agenthas X milliequivalents of charge per gram of chemical agent at pH 4.5.

A hydrophobic outer surface on the intermediate transfer member isdesirable as it assists in the eventual transfer of the residue film tothe substrate. Such a hydrophobic outer surface or release layer is,however, undesirable during ink image formation, among other reasonsbecause bead-like ink droplets cannot be stably transported by a fastmoving intermediate transfer member, and because they result in athicker film with less coverage of the surface of the substrate.

In some embodiments, the hydrophobic release layer may comprisepositively chargeable molecules or moieties, such as amino silicones asfurther detailed in PCT application No. PCTIB2013/051751, published asWO 2013/132438.

The presently claimed invention sets out to preserve, or freeze, thethin pancake shape of each ink droplet, that is caused by the flatteningof the ink droplet on impacting the surface of the intermediate transfermember, despite the hydrophobicity of the surface of the intermediatetransfer member, while also facilitating transfer of the ink droplet sofrozen to a substrate.

Although so-called “wetting agents”, viz. agents that reduce the surfacetension of ink droplets on a particular surface, are known in the artfor use with other types of transfer members or for use with non-aqueousinks on hydrophobic surfaces, these are often unsatisfactory in thecontexts in which they are used and unsatisfactory for use with thecombination of aqueous inks on hydrophobic transfer member surfaces.Inter alia, the use of wetting agents can result in droplets on thesurface of the transfer manlier that undesirably spread or have roughedges, which results in a printed substrate of less than ideal quality.

The present invention facilitates printing using an aqueous ink and anintermediate transfer member having a hydrophobic surface, by applyingto the surface of the transfer member to which the ink is applied i.e.by applying to the hydrophobic release layer—a small amount, preferablyin the form of a thin layer, of chemical agent that reduces the tendencyof the aqueous inkjet ink droplet that has been printed onto the releaselayer to contract. Measurements show that the contact angle of water ona hydrophobic release layer so treated remains high, indicating that, incontrast to wetting agents, treatment with the chemical agent does notresult in a loss of surface tension. Therefore, the chemical agent ofthe present disclosure advantageously reduces droplet contraction,without causing an undesired spreading of the droplet much beyond itsinitial impact pancake shape. Electron micrographs of aqueous inkjetinks printed onto a release layer so treated, then dried while still onthe release layer and then transferred to a paper substrate show thatthe edges of such ink droplets are sharper than the edges of inkdroplets transferred to paper by other means. The chemical agent thusfixes the ink film to the release layer, although it will he appreciatedthat such fixation is weaker than the subsequent adhesion of the resinin the ink film residue to the substrate.

Application of the chemical agent in accordance with some embodiments ofthe invention results in positive charge on at least portions of therelease layer, This may be achieved, for example, by applying to thesurface of the intermediate transfer member molecules having one or moreBronsted base functional groups and in particular nitrogen-containingmolecules, under conditions in which the molecules bear positive charge.Suitable positively charged or chargeable groups include primary amines,secondary amines, tertiary amines, and quaternary ammonium moieties, andthe chemical agent may contain more than one such group. Such groups canbe covalently bound to polymeric backbones or constitute part of suchbackbones, as is the case in, for example, polyethylene imine (bothlinear and branched, the latter of which may contain all three types ofamines), poly(diallyldimethylammonium chloride), poly(4-vinylpyridine),polyallylamine, vinyl pyrrolidone-di mealy laminopropyl methacry ami deco-polymer, vinyl caprolactam-dimethylaminopropyl methacryamidehydroxyethyl methacrylate copolymer, quaternized copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate with diethyl sulfate,guar hydroxypropyltrimonium chloride, and hydroxypropyl guarhydroxypropyltrimonium chloride. Classes of polycations that may be usedas chemical agents to he applied to the release layer include, forinstance, polyamines, including poly(amino methacrylates) includingpoly(dialkylaminoalkyl methacrylates) such as poly(dimethylaminoethylmethacrylate) and poly(diethylaminoethyl methacrylate), polyvinylamines,polyvinyl-pyridines including quaternary polyvinylpyridines such aspoly(N-ethyl-4-vinylpyridine), poly(vinyibenzyltrimethylamines),polyallylamines such as poly(allylamine hydrochloride) (PAH) andpoly(diallyldialklylamines) such as poly(diallyldimethylammoniumchloride), polyamidoamines, polyimines including polyalkyleneimines suchas polyethyleneimines, polypropyleneimines and ethoxylatedpolyethyleneimines, and polycationic polysaccharides such as cationicstarch and chitosan, as well as copolymers, salts, derivatives andcombinations of the preceding, among various others. It will beappreciated that the chemical agent should be chosen to withstand thetemperature at which the printing process is carried out (see detaileddescription of such a process below), at least for a time sufficient toallow jetting and drying of the ink on the dried chemical agent, aperiod of time which is usually on the order of a few seconds.

Whether the positively chargeable functional groups of the molecules onthe release layer are part of the release layer itself (e.g., if therelease layer has protonatable elastomers such as amino silicones) orwhether they are part of the chemical agent applied on the electricallyneutral hydrophobic release layer (e.g. silanol terminated silicones),such positively chargeable functional groups of the molecules on therelease layer may interact with negatively charged functional groups ofmolecules of the ink. Suitable negatively charged or negativelychargeable groups include carboxylic acid groups (—COOH), includingacrylic acid groups (—CH₂═CH—COOH) and methacrylic acid groups(—CH₂═C(CH₃)—COOH), and sulfonic acid groups (—SO₃H). Such groups can becovalently bound to polymeric backbones; for example styrene-acryliccopolymer resins have carboxylic acid functional groups which readilylose protons to yield negatively-charged moieties.

The contacting of the surface of the intermediate transfer member with apositively charged conditioning/treatment solution or dispersion can beviewed as applying molecules that are adsorbed to the surface of theintermediate transfer member and present a net positive charge withwhich some of the negatively charged molecules in the ink may interact.It will be appreciated that the chemical agent should preferably bequickly adsorbed onto the release layer, e.g. by electrostaticattraction between the charged nitrogen atoms and hydroxyl groupspresent in the release layer as a result of the condensation reactionemployed to form the release layer, but that the strength of thisattraction should be less than the attraction between the chemical agentand the ink and the attraction between the ink the substrate.

Thus, among the factors to be taken into account in selecting thechemical agent for use in treating the release layer, charge density andmolecular weight have been found to be two important parameters. Incases in which the positive charge is provided by protonation ofnitrogen atoms (or by the presence of quaternary ammonium ions), thepercentage of nitrogen atoms in the polymer as a function of the weightof the polymer may serve as a proxy for charge density. Thus, forexample, it has been found that guar hydroxylpropyltrimonium chloridehaving a high molecular weight but relatively small percentage ofnitrogen atoms (1.4 wt. %), and thus a relatively low charge density,nevertheless functions as an effective chemical agent at a printingtemperature of 150° C. On the other hand, polyethylene imines, whichhave a much higher percentage of nitrogen (around 32% in linear form),were found to be effective with an average molecular weight of as low as800 in one case, as well as with higher average molecular weights. Thuswhile the charge densities of PEI polymers are generally in the range of16-20 meq/g of material, in one case a PEI having a charge density of 8meq/g was found to be suitable. Other suitable polymers includepoly(diallyldimethylammonium chloride)

polyallylamine

and poly(4-vinylpyridine)

persons skilled in the art will appreciate other suitable polymers.However, as noted above, charge density alone is not determinative: asreported below, a large number of charged species, but of smaller sizethan the polymers tested, were also tested and found to be far lesseffective than the polymers. Thus, in some embodiments, the chemicalagent has an average molecular weight of at least 2,000, at least10,000, and preferably at least 25,000. Of the small molecules tested,the one which yielded the best results waspentahydroxy(tetradecanoato)di-chromium The chemical agent should alsobe water dispersible, preferably water soluble, and should be able toquickly (i.e. in under a second from application to the release layer,e.g. in 0.5, 0.1, 005, 0.01, 0,005 or 0.001 seconds or less, andpreferably instantaneously) affix itself to the release layer.

As noted above, the hydrophobic release layer of the intermediatetransfer member may be silicon-based, e.g. the product of cross-linkingby condensation a silanol-terminated polydialkylsiloxane, such as apolymer of formula (I):

where R1 to R6 are each independently a C₁ to C₆ hydrocarbon group(saturated or unsaturated, linear or branched), R7 is selected from thegroup consisting of OH, H or a C₁ to C₆ hydrocarbon group (saturated orunsaturated, linear and/or branched); and, n is an integer from 50 to400. In some cases, n is an integer between 200 and 350. In someinstances, the silicone has a molecular weight of between 15,000 to26,000 g/mole, e.g. 16,000 to 23,000 a/mol, prior to crosslinking. Inone example of such a material, the silicone is a silanol-terminatedpolydimethylsiloxane, i.e. R1 to R6 are all CH₃ and R7=OH. Thecrosslinker, which may be present in an amount between e.g. 5 to 20 wt.%, such as 9 to 12 wt. %, relative to the polymer prior to crosslinking,may be a oligomeric condensate of a polyethylsilicate monomer, such asSilopren E 0.7 (Monientive), PS1023 (Gelest) and Ethylsilicate 48(Colcoat). Preferably, the silicon polymer is made by condensationcuring.

Release layers so prepared are amenable to pre-treatment with aconditioning agent as afore mentioned. Although in principle the aqueousink may be jetted onto the chemical agent-treated release layer whilethe chemical agent is still wet in solution, it is preferable that thechemical agent generally be dry prior to the jetting of the ink, and inpractice this is the case, as the conditioning agent may be immediatelyremoved following application (e.g., by air flow) and release layer willgenerally be heated, resulting in drying of the chemical agent solutionbefore jetting of the ink occurs, so that the ink droplets are directedonto a substantially dry surface.

Aqueous inkjet inks suitable for use in conjunction with embodiments ofthe present invention contain water-soluble or water-dispersiblecolorants, e.g. dyes or nano pigments, and a water-dispersible orwater-soluble polymeric resin, As noted above, such resins, such asstyrene-acrylic copolymers, contain moieties such as free carboxylgroups that are negatively chargeable (i.e. they have protons which theywill readily give up) and are generally negatively charged under theconditions of use (e.g. at alkaline pH). In addition to being suitablefor jetting from an inkjet printhead, the inks should also be formulatedso as to transfer well from the intermediate transfer member to thesubstrate under the conditions of use, and preferably should besusceptible to having most or substantially all of the solvent and, ifpresent, other volatiles removed therefrom prior to the transfer.

It has been found that contacting the hydrophilic release layer with asmall amount of positively charged polymeric material so that thepositively charged material is disposed thereupon (e.g. as a thin layer)suitably reduces the tendency of the aqueous inkjet ink droplet that hasbeen jetted onto the release layer to contract. In this connection, itshould be noted that not all positively-charged materials are suitableto this end. For example, low molecular weight quaternary amines werefound to provide little improvement in the transfer of the ink to apaper substrate, whereas polymeric compounds containing aminessignificantly improved such transfer. An example of a suitable inkformulation is described below.

The chemical agent may be applied to the release layer as a dilute,preferably aqueous, solution or dispersion, for example at aconcentration of about 1 wt. %, 0.5 wt. %, 0.3 wt. %, 0.2 wt. % or 0.1wt. % or less of the chemical agent, preferably under conditions inwhich the chemical agent is positively charged, e.g. amine nitrogenatoms contained therein are in protonated form as the correspondingammonium ions. The solution or dispersion may be and preferably isheated to evaporate the solvent prior to the ink image formation,whereby the ink droplets are directed onto a substantially dry surface,Furthermore, it is only necessary to apply a sufficient amount of thechemical agent so that, once dry on the release layer, the chemicalagent will retard the contraction of aqueous inkjet ink droplets thathave been jetted on the release layer, without substantially affectingthe release properties of the release layer. The chemical agent soapplied and dried may thus form a thin layer, preferably not more than afew nanometers thick. Application of excess solution containing thechemical agent will not only increase the time required for the solutionto dry before the ink is printed onto the release layer but, if too muchchemical agent is applied, may also reduce the effectiveness of thetransfer of the dried ink to the substrate. In some embodiments, thechemical agent on which ink has been printed will transfer with that inkto the substrate:, forming a sandwich in which the chemical agent restson the ink which lies on the substrate. Since the ink itself willtypically form a layer having a thickness several orders of magnitudegreater than that of the chemical agent (e.g. ˜100-400 nm thicknessafter drying), the presence of a layer of chemical agent a fewnanometers thick on ink on the substrate will not appreciably affect theproperties of that ink, such as glossiness or optical density. This isanother reason why the amount of chemical agent should ideally be keptto a minimum: an unnecessarily large amount of the chemical agentpresent on the release layer may result in excess chemical agent on theink that is transferred to the substrate. Moreover, since even underideal circumstances some of the chemical agent may remain on the releaselayer, the avoidance of use of excess chemical agent will minimize thebuild-up of such agent on the release layer, and will lengthen the timerequired between cleanings of the release layer.

Solutions or dispersion containing the chemical agent may applied to therelease layer in a manner known in the art for applying liquids to solidsurfaces, such as by spraying or by use of a roller; it is preferablethat the chemical agent be applied evenly to the release layer or evenedout after application and before jetting of the ink, preferably beforedrying of the chemical agent. It will be appreciated that a rod, such asa wire-wound metering rod (Mayer rod), may be employed in theapplication process. Methods known in the art for regulating thethickness of such a liquid layer may be utilized, and additionalmachinery may be employed to this end. In some embodiments, the chemicalagent is applied to the release layer by undulations from a fountain orspraying and then evened using a metering roller or removed from thetransfer member shortly following its exposure thereto (e.g. by wipingor using an air flow). In some embodiments, the metering roller is achrome roller, i.e. it is made of chrome or is chrome-plated. In oneembodiment, the chrome roller is a forward roller that works inconjunction with a metering roller that may be made, for example, frompolyurethane. The chrome roller may be equipped with an internal coolingsystem in order to keep its temperature lower than that of the releaselayer. As mentioned below, it has been found that placing a drop of 0.3wt. % PEI solution on a release layer and immediately applying a streamof air to both spread and dry the solution within a few seconds,followed by jetting of an ink onto the release layer and pressing asubstrate against the release yielded good transfer of the ink to thesubstrate in the areas of the release layer which were contacted withPEI. Thus in some embodiments it is sufficient that after removal of thesolvent, the chemical agent be present in a layer of a few molecules'thickness or even a monolayer.

Although in principle the aqueous inkjet ink may be jetted onto thechemical agent-coated release layer while the chemical agent is stillwet in solution, in practice the chemical agent will generally be dryprior to the jetting of the ink, as the release layer will generally beheated, resulting in drying of the chemical agent solution beforejetting of the ink occurs, so that the ink droplets are directed onto asubstantially dry surface.

The ratio of charges in the ink droplet to the charges in the region ofthe chemical agent upon which the ink droplet rests may be small, butthis need not be the case. Assuming an initial layer of chemicalagent-containing solution of 1 micron thickness containing 0.2 wt. % ofthe chemical agent, 1 square meter of release layer contains 1 g ofchemical agent solution or, after drying, 2 mg of dr chemical agent.Assuming a single ink drop of 12 picoliter volume then has a 30 micronradius containing 7.5 wt. % charged resin, then the area covered by thisdrop will be approximately 2.83×10⁻⁹ square meters, so that one drop ofink covers 5.65 picograms of the chemical agent. If the chemical agenthas a charge density of 6 milliequivalents per gram, then one drop ofink covers 3.39×10⁻¹⁴ amines of the chemical agent. Since one drop has amass of 12 ng and contains 7.5 wt. % of resin, it contains 0.9 nanogramsof resin. If the resin has acid number 86 mg KOH/g then its chargedensity is 1.54 meq/g, thus it contains 1.38 picoequivalents of carboxylgroups, giving a carboxyl/amine ratio of approximately 40. Using thissame calculation, if one assumes an ink drop of the same volume andresin concentration but having a charge density of 12 meq/g, i.e. twicethe charge density, then the carboxyl/amine ratio would be 80. Similarcalculations can be made for different charge densities of the chemicalagent, e.g. if the charge density of the chemical agent is 18, and theother parameters are assumed to be the same.

The calculations in the previous paragraph indicate that any interactionbetween negative charges in the resin in the ink and positive charges inthe chemical agent on the release layer cannot be stoichiometric. It hasbeen found experimentally that if a single droplet of a dilutepolyethylene imine (PEI) solution is dropped onto the hydrophobicsurface (silanol-terminated dimethylpolysiloxane) and immediately blownaway and evaporated by a stream of high pressure air, ink droplets willonly thereafter adhere without beading up on the pans of the surfacethat have come into contact with the dilute PEI solution, even thoughcontact between the PEI solution and the hydrophobic surface was onlyfor a brief instant. As such application can only leave a layer having athickness of a very few molecules (possibly only a monolayer), thisresult confirms that the interaction with ink cannot be a stoichiometricchemical one, having regard to the significant difference between theMSS of the PEI layer and the mass of the ink droplets.

As the amount of charge on the transfer member is too small to attractmore than a small number of charged resin particles in the ink, it isbelieved that the concentration and distribution of the charged resinparticles in the drop is not substantially changed as a result ofcontact with the chemical agent on the release layer.

It is also believed that the concentration and distribution of thecharged resin particles in such an ink droplet is not substantiallychanged as a result of contact with the release layer per se, if therelease layer is positively chargeable.

Chemical agents in accordance with embodiments of the present inventionmay also be characterized by their effect on the contact angle of water,In particular, it has been found that when the hydrophobic release layeris coated with a thin layer (˜1-2 nm) of chemical agent (e.g.polyethylene imine) in accordance with embodiments of the invention, thecontact angle of a drop of distilled water on the hydrophobic releaselayer does not change in comparison to a drop of water on an uncoatedlayer. This indicates that the surface energy, and thus the surfacetension of the water droplet, is essentially unaffected by the chemicalagent. This is in contrast to the action of conventional wetting agentsas used in prior art processes, which by definition affect the surfaceenergy of the transfer surface and give rise to droplets havingsignificantly lower contact angles. It will also be appreciated that theeffect of some conventional wetting agents on the hydrophobic releaselayer were tested with aqueous ink and found to yield transfer to apaper substrate that was no better than if the release layer had beenuntreated.

It has been found, surprisingly, that the application of a chemicalagent to a hydrophobic release layer in accordance with embodiments ofthe invention has a profound effect on the shape of the ink dropletsafter the droplets stabilize. To revert from a pancake or disk-likeshape to a spherical globule, surface tension needs to peel the surfaceof the ink droplet away from the surface of the intermediate transfermember. However, within the time frame of the printing process describedherein—i.e. several seconds from the jetting of the ink onto theintermediate transfer merriber until the solvent is evaporated from theink and the ink is then transferred to the substrate—the ink dropletdoes not revert from a pancake back to a globule on release layerscoated with the chemical agent. Without wishing to be bound by theory itis believed that the intermolecular forces between the chemical agent onthe release layer and the resin in the ink resist such separation of thesurface of the droplet from the surface of the release layer, resultingin a relatively fiat droplet of ink which remains flatter to asignificantly greater extent than a droplet of the same volume depositedon the same surface without such conditioning. Furthermore, since inareas that are not reached by the droplet the effective hydrophobicnature of the transfer member is maintained, there is little or nospreading of the droplet above that achieved in the initial impact andthe boundaries of the droplet are distinct; in other words there is nowetting by the ink droplets of the surface of the intermediate transfermember, thus resulting in droplets having a regular rounded outline.

In some embodiments of the invention, the intermediate transfer memberis a flexible blanket of which the outer surface is the hydrophobicouter surface upon which the ink image is formed. It is howeveralternatively possible for the intermediate transfer member to beconstructed as a drum.

In accordance with a feature of some embodiments of the invention, priorto transferring the residue film onto the substrate, the ink image isheated to a temperature at which the residue film of resin and coloringagent that remains after evaporation of the aqueous carrier is renderedtacky (e.g. by softening of the resin). The temperature of the tackyresidue film on the intermediate transfer member may be higher than thetemperature of the substrate, whereby the residue film cools duringadhesion to the substrate.

By suitable selection of the thermo-rheological characteristics of theresidue film the effect of the cooling may be to increase the cohesionof the residue film, whereby its cohesion exceeds its adhesion to thetransfer member so that, when brought into contact with the substratee.g. at an impression station (see below), for which it has greateraffinity than for the release layer, substantially all of the residuefilm is separated from the intermediate transfer member and impressed asa film onto the substrate. In this way, it is possible to ensure thatthe residue film is impressed on the substrate without significantmodification to the area covered by the film nor to its thickness.

Upon transfer of the ink image from the release layer to the substrate,some, often most, and often nearly all of the chemical agent upon whichink has been jetted will transfer with the image to the substrate,resulting in an ink image on the substrate having a thin (generally 1-10nm thick) layer of the chemical agent thereupon. As will be appreciatedby persons skilled in the art, the presence of the chemical agent may bedetected through various methods, such as X-ray photoelectronspectroscopy, or by dissolving a portion of the chemical agent and thendetecting its present in the solution by HPLC or IR spectroscopy.

The ink used in conjunction with the chemical agent on the release layerpreferably utilizes an aqueous carrier, which reduces safety concernsand pollution issues that occur with inks that utilize volatilehydrocarbon carrier. In general, the ink must have the physicalproperties that are needed to apply very small droplets close togetheron the transfer member.

Other effects that may contribute to the shape of the droplet remainingin the flattened configuration are quick heating of the droplets toincrease their its viscosity; the presence of a polymeric conditioningagent that reduces the hydrophobic effect of the silicone layer; and thepresence in the ink of a surfactant that reduces the surface tension ofthe ink.

In general, ink jet printers require a trade-off between purity of thecolor, the ability to produce complete coverage of a surface and thedensity of the ink-jet nozzles. If the droplets (after beading) aresmall, then, in order to achieve complete coverage, it is necessary tohave the droplets close together. However, it is very problematic (andexpensive) to have the droplets closer than the distance between pixels.By forming relatively flat droplet films that are held in place in themanner described above, the coverage caused by the droplets can be closeto complete.

In some instances, the carrier liquid in the image is evaporated fromthe image after it is formed on the transfer member. Since the colorantin the droplets is distributed within the droplet, either as a solution(e.g. in the case of a dye) or as a dispersion (e.g. in the case of apigment), the preferred method for removal of the liquid is by heatingthe image, either by heating the transfer member or by external heatingof the image after it is formed on the transfer member, or by acombination of both. In some instances, the carrier is evaporated byblowing a heated gas (e.g. air) over the surface of the transfer member.

In some instances, different ink colors are applied sequentially to thesurface of the intermediate transfer member and a heated gas is blownonto the droplets of each ink color after their deposition but beforedeposition on the intermediate transfer member of the next ink color. Inthis way, merging of ink droplets of different colors with one anotheris reduced.

In some instances, the polymer resin used in the ink is a polymer thatenables the ink to form a residue film when it is heated (the termresidue film is used herein to refer to the ink droplets afterevaporation of the liquid carrier therefrom). Acrylic-styreneco-polymers with an average molecular weight around 60,000, for example,have been found to be suitable. Preferably all of the liquid in the inkis evaporated, however, a. small amount of liquid, that does notinterfere with the forming of a residue film may be present. Theformation of a residue film has a number of advantages. The first ofthese is that when the image is transferred to the final substrate all,or nearly all, of the image can be transferred. This allows in somecases for a system without a cleaning station for removing residues fromthe transfer member. It also allows for the image to be attached to thesubstrate with a nearly constant thickness of the image covering thesubstrate. Additionally, it prevents the penetration of the imagebeneath the surface of the substrate.

In general, when an image is transferred to or formed on a substratewhile it is still liquid, the image penetrates into the fibers of thesubstrate and beneath its surface. This causes uneven color and areduction in the depth of the color, since some of the coloring agent isblocked by the fibers. In some instances, the residue film is very thin,preferably between 10 nm and 800 nm and more preferably between 50 nmand 500 nm. Such thin films are transferred intact to the substrate and,because they are so thin, replicate the surface of the substrate byclosely following its contours. This results in a much smallerdifference in the gloss of the substrate between printed and non-printedareas.

When the residue film reaches a transfer station at which it istransferred from the intermediate transfer member to the finalsubstrate, it is pressed against the substrate, having preferablypreviously been heated to a temperature at which it becomes tacky inorder to attach itself to the substrate.

Preferably, the substrate, which is generally not heated, cools theimage so that it solidifies and transfers to the substrate withoutleaving any of residue film on the surface of the intermediate transfermember. For this cooling to be effective, additional constraints areplaced on the polymer in the ink

The fact that the carrier is termed an aqueous carrier is not intendedto preclude the presence of certain organic materials in the ink, inparticular, certain innocuous water miscible organic material and/orco-solvents, such as ethylene glycol or propylene glycol.

As the outer surface of the intermediate transfer member is hydrophobic,there may be little (<1.5%) or substantially no swelling of the transfermember due to absorption of water from the ink; such swelling is knownto distort the surface of transfer members in commercially availableproducts utilizing silicone coated transfer members and hydrocarboncarrier liquids. Consequently, the process described above may achieve ahighly smooth release surface, as compared to intermediate transfermember surfaces of the prior art.

As the image transfer surface is hydrophobic, and therefore not waterabsorbent, substantially all the water in the ink should be evaporatedaway if wetting of the substrate is to be avoided. It will beappreciated that the inclusion of certain co-solvents, such as ethyleneglycol or propylene glycol, which have higher boiling points than water,may reduce the rate at which the solvent evaporates relative to thesituation in which water is the only solvent. However, the ink dropletson the transfer member are of sufficiently small thickness relative totheir surface area, and are usually heated at a temperature for a time,sufficient to allow for evaporation of substantially all of the solventprior to transfer to the substrate.

DRAWINGS

Embodiments of invention will now be described further, by way ofexamples, and with reference to the accompanying drawings showing theoperation of a printing system in which the presently claimed inventionmay be practiced, in which:

FIG. 1 is an exploded schematic perspective view of a printing system inaccordance with which an embodiment of the invention may he used;

FIG. 2 is a schematic vertical section through the printing system ofFIG. 1, in which the various components of the printing system are notdrawn to scale;

FIG. 3 is a schematic representation of a printing system of theinvention in accordance with which an embodiment of the invention may beused;

FIGS. 4, 5A, 5B, 5C and 5D are scans of paper onto which ink wastransferred from a hydrophobic release layer, illustrating the effectsof contacting the release layer with different (or no) chemical agentsprior to jetting of the ink onto the release layer.

FIG. 6 is a ramped-down temperature sweep plot of dynamic viscosity as afunction of temperature, for several ink formulations of the presentinvention;

FIG. 7 is a ramped-down temperature sweep plot of dynamic viscosity as afunction of temperature, for several ink formulations of the presentinvention, vs. several commercially available inkjet inks; and

FIG. 8 is a magnified view of the plot of FIG. 7, for owe viscosities.

GENERAL OVERVIEW OF A PRINTING APPARATUS

The printing system shown in FIGS. 1 and 2 essentially comprises threeseparate and mutually interacting systems, namely a blanket system 100,an image forming system 300 above the blanket system 100 and a substratetransport system 500 below the blanket system 100.

The blanket system 100 comprises an endless belt or blanket 102 thatacts as an intermediate transfer member and is guided over two rollers104, 106. An image made up of dots of an aqueous ink is applied by imageforming system 300 to an upper run of blanket 102 at a location referredherein as the image forming station. A lower run selectively interactsat two impression stations with two impression cylinders 502 and 504 ofthe substrate transport system 500 to impress an image onto a substratecompressed between the blanket 102 and the respective impressioncylinder 502, 504. As will be explained below, the purpose of therebeing two impression cylinders 502, 504 is to permit duplex printing. Inthe case of a simplex printer, only one impression station would beneeded. The printer shown in FIGS. 1 and 2 can print single sided printsat twice the speed of printing double sided prints. In addition, mixedlots of single and double sided prints can also be printed.

In operation, ink images, each of which is a mirror image of an image tobe impressed on a final substrate, are printed by the image formingsystem 300 onto an upper run of blanket 102. In this context, the term“run” is used to mean a length or segment of the blanket between any twogiven rollers over which the blanket is guided. While being transportedby the blanket 102, the ink is heated to dry it by evaporation of most,if not all, of the liquid carrier. The ink image is furthermore heatedto render tacky the film of ink solids remaining after evaporation ofthe liquid carrier, this film being referred to as a residue film, todistinguish it from the liquid film formed by flattening of each inkdroplet. At the impression cylinders 502, 504 the image is impressedonto individual sheets 501 of a substrate which are conveyed by thesubstrate transport. system 500 from an input stack 506 to an outputstack 508 via the impression cylinders 502, 504. Though not shown in thefigures, the substrate may be a continuous web, in which case the inputand output stacks are replaced by a supply roller and a delivery roller.The substrate transport system needs to be adapted accordingly, forinstance by using guide rollers and dancers taking slacks of web toproperly align it with the impression station.

Image Forming System

The image forming system 300 comprises print bars 302 which may each beslidably mounted on a frame positioned at a fixed height above thesurface of the blanket 102. Each print bar 302 may comprise a strip ofprint heads as wide as the printing area on the blanket 102 andcomprises individually controllable print nozzles. The image formingsystem can have any number of bars 302, each of which may contain anaqueous ink of a different color.

As some print bars may not be required during a particular printing job,the heads can be moved between an operative position (at which the barremains stationary), in which they overlie blanket 102 and aninoperative position (at which the bar can be accessed for maintenance).

Within each print bar, the ink may be constantly recirculated, filtered,degased and maintained at a desired temperature and pressure, as knownto the person skilled in the art without the need for more detaileddescription.

As different print bars 302 are spaced from one another along the lengthof the blanket, it is of course essential for their operation to becorrectly synchronized with the movement of blanket 102.

If desired, it is possible to provide a blower following each print bar302 to blow a slow stream of a hot gas, preferably air, over theintermediate transfer member to commence the drying of the ink dropletsdeposited by the print bar 302. This assists in fixing the dropletsdeposited by each print bar 302, that is to say resisting theircontraction and preventing their movement on the intermediate transfermember, and also in preventing them from merging into droplets depositedsubsequently by other print bars 302.

Blanket and Blanket Support System

The blanket 102, in one variation, is seamed. In particular, the blanketis formed of an initially flat strip of which the ends are fastened toone another, releasably or permanently, to form a continuous loop oftenreferred to as a belt. A releasable fastening may be a zip fastener or ahook and loop fastener that lies substantially parallel to the axes ofrollers 104 and 106 over which the blanket is guided. A permanentfastening may be achieved by the use of an adhesive or a tape.Alternatively, the belt may be seamless.

In order to avoid a sudden change in the tension of the blanket as theseam passes over rollers or other parts of the support system, it isdesirable to make the seam, as nearly as possible, of the same thicknessas the remainder of the blanket.

The primary purpose of the blanket is to receive an ink image from theimage forming system and to transfer that image dried but undisturbed tothe impression stations. To allow easy transfer of the ink image at eachimpression station, the blanket has a thin upper release layer that ishydrophobic, suitable examples of which have been described above. Theouter surface of the transfer member upon which the ink can be appliedmay comprise a silicone material. Under suitable conditions, a silanol-,sylyl- or silane-modified or terminated polydialkylsiloxane material hasbeen found to work well.

The strength of the blanket can be derived from a support orreinforcement layer. In one instance, the reinforcement layer is formedof a fabric. If the fabric is woven, the warp and weft threads of thefabric may have a different composition or physical structure so thatthe blanket should have, for reasons to be discussed below, greaterelasticity in its widthways direction (parallel to the axes of therollers 104 and 106) than in its lengthways direction.

The blanket may comprise additional layers between the reinforcementlayer and the release layer, for example to provide conformability andcompressibility of the release layer to the surface of the substrate.Other layers provided on the blanket may act as a thermal reservoir or athermal partial barrier and/or to allow an electrostatic charge to theapplied to the release layer. An inner layer may further be provided tocontrol the frictional drag on the blanket as it is rotated over itssupport structure. Other layers may be included to adhere or connect theafore-mentioned layers one with another or to prevent migration ofmolecules therebetween.

The blanket support system may comprise thermally conductive supportplates 130 forming a continuous flat support surface both on the topside and bottom side of the support frame. Electrical heating elementscan be inserted into transverse holes of the plates to apply heat to theplates 130 and through plates 130 to the blanket 102. Other means forheating the blanket will occur to the person of skill in the art and mayinclude heating from below, above, or within the blanket itself.

Also mounted on the blanket support frame are two pressure or niprollers 140, 142 which can be raised and lowered from the lower run ofthe blanket. The pressure rollers are located on the underside of thesupport frame in gaps between the support plates 130 covering theunderside of the frame. The pressure rollers 140, 142 are alignedrespectively with the impression cylinders 502, 504 of the substratetransport system. Each impression roller and corresponding pressureroller, when both are engaged with the blanket passing therebetween,form an impression station.

In some instances, the blanket support system further comprises acontinuous track, which can engage formations on the side edges of theblanket to maintain the blanket taut in its width ways direction. Theformations may be spaced projections, such as the teeth of one half of azip fastener sewn or otherwise attached to the side edge of the blanket.Alternatively, the formations may be a continuous flexible bead ofgreater thickness than the blanket. The lateral track guide channel mayhave any cross-section suitable to receive and retain the blanketlateral formations and maintain it taut. To reduce friction, the guidechannel may have rolling bearing elements to retain the projections orthe beads within the channel.

In order for the image to be properly formed on the blanket andtransferred to the final substrate and for the alignment of the frontand back images in duplex printing to be achieved, a number of differentelements of the system must be properly synchronized. In order toposition the images on the blanket properly, the position and speed ofthe blanket must be both known and controlled. For this purpose, theblanket can be marked at or near its edge with one or more markingsspaced in the direction of motion of the blanket. One or more sensors107 sense the timing of these markings as they pass the sensor. Thespeed of the blanket and the speed of the surface of the impressionrollers should be the same, for proper transfer of the images to thesubstrate from the transfer blanket. Signals from the sensor(s) 107 aresent to a controller 109 which also receives an indication of the speedof rotation and angular position of the impression rollers, for examplefrom encoders on the axis of one or both of the impression rollers (notshown). Sensor 107, or another sensor (not shown) also determines thetime at which the seam of the blanket passes the sensor. For maximumutility of the usable length of the blanket, it is desirable that theimages on the blanket start as close to the seam as feasible.

A printing system operating on the same principle as that of FIG. 1 butadopting an alternative architecture is shown in FIG. 3. The printingsystem of FIG. 3 comprises an endless belt 210 that cycles through animage forming station 212, a drying station 214, and a transfer station216. The image forming. station 212 being similar to the previouslydescribed image forming system 300, illustrated in FIG. 1.

In the image forming station 212 four separate print bars 222incorporating one or more print heads, that use inkjet technology,deposit aqueous ink droplets of different colors onto the surface of thebelt 210. Though the illustrated embodiment has four print bars eachable to deposit one of the typical four different colors (namely Cyan(C), Magenta (M), Yellow (Y) and Black (K)), it is possible for theimage forming station to have a different number of print bars and forthe print bars to deposit different shades of the same color (e.g.various shades of grey including black) or for two print bars or more todeposit the same color (e.g. black). Following each print bar 222 in theimage forming station, an intermediate drying system 224 is provided toblow hot gas (usually air) onto the surface of the belt 210 to dry theink droplets partially. This hot gas flow may also assist in preventingblockage of the inkjet nozzles and additionally prevents the droplets ofdifferent color inks on the belt 210 from merging into one another. Inthe drying station 214, the ink droplets on the belt 210 are exposed toradiation and/or hot gas in order to dry the ink more thoroughly,driving off most, if not all, of the liquid carrier and leaving behindonly a layer of resin and coloring agent which is heated to the point ofbeing rendered tacky.

In the transfer station 216, the belt 210 passes between an impressioncylinder 220 and a blanket cylinder 218 that carries a compressibleblanket 219. The length of the blanket is equal to or greater than themaximum length of a sheet 226 of substrate on which printing is to takeplace. The impression cylinder 220 has twice the diameter of the blanketcylinder 218 and can support two sheets 226 of substrate at the sametime. Sheets 226 of substrate are carried by a suitable transportmechanism (not shown) from a supply stack 228 and passed through the nipbetween the impression cylinder 220 and the blanket cylinder 218. Withinthe nip, the surface of the belt 220 carrying the tacky ink image ispressed firmly by the blanket on the blanket cylinder 218 against thesubstrate so that the ink image is impressed onto the substrate andseparated neatly from the surface of the belt. The substrate is thentransported to an output stack 230. In some embodiments, a heater 231may be provided shortly prior to the nip between the two cylinders 218and 220 of the image transfer station to assist in rendering the inkfilm tacky, so as to facilitate transfer to the substrate.

It is important for the belt 210 to move with constant speed through theimage forming station 212 as any hesitation or vibration will affect theregistration of the ink droplets of different colors. To assist inguiding the belt smoothly, friction is reduced by passing the belt overrollers 232 adjacent each print bar 222 instead of sliding the belt overstationary guide plates. The rollers 232 need not be precisely alignedwith their respective print bars. They may be located slightly (e.g. afew millimeters) downstream of the print head jetting location. Thefrictional forces maintain the belt taut and substantially parallel toprint bars. The underside of the belt may therefore have high frictionalproperties as it is only ever in rolling contact with all the surfaceson which it is guided. The lateral tension applied by the guide channelsneed only be sufficient to maintain the belt 210 flat and in contactwith rollers 232 as it passes beneath the print bars 222. Aside from theinextensible reinforcement/support layer, the hydrophobic releasesurface layer and high friction underside, the belt 210 is not requiredto serve any other function, It may therefore be a thin lightinexpensive belt that is easy to remove and replace, should it becomeworn.

To achieve intimate contact between the hydrophobic release layer andthe substrate, the belt 210 passes through the transfer station 216which comprises the impression and blanket cylinders 220 and 218. Thereplaceable blanket 219 releasably clamped onto the outer surface of theblanket cylinder 218 provides the confomiability required to urge therelease layer of the belt 210 into contact with the substrate sheets226. Rollers 253 on each side of the transfer station ensure that thebelt is maintained in a desired orientation as it passes through the nipbetween the cylinders 218 and 220 of the transfer station 216.

The above description of the apparatus illustrated in FIG. 3 issimplified and provided only for the purpose of enabling anunderstanding of printing systems and processes with which the presentlyclaimed invention may be used. For a successful printing system, thecontrol of the various stations of the printing system is important butneed not be considered in detail in the present context.

In order for the ink to separate neatly from the surface of the belt 210it is necessary for the latter surface to have a hydrophobic releaselayer. In the arrangement of FIG. 1, this hydrophobic release layer isformed as part of a thick blanket that also includes a compressibleconformability layer which is necessary to ensure proper contact betweenthe release layer and the substrate at the impression station. Theresulting blanket is a very heavy and costly item that needs to bereplaced in the event a failure of any of the many functions that itfulfills. In the arrangement of FIG. 3, the hydrophobic release layerforms part of a separate element from the thick blanket 219 that isneeded to press it against the substrate sheets 226. In FIG. 3, therelease layer is formed on the flexible thin inextensible belt 210 thatis preferably fiber reinforced for increased tensile strength in itslengthwise dimension.

Blanket Pre-Treatment

FIG. 1 shows schematically a roller 190 positioned on the external sideof the blanket immediately before roller 106, according to an embodimentof the invention. Such a roller 190 may be used to apply a thin film ofpre-treatment solution containing a chemical agent, for example a dilutesolution of a positively charged polymer according to the teachingsherein disclosed, to the surface of the blanket. Preferably, the solventis totally removed from the film by the time it reaches the print barsof the image forming system, to leave behind a very thin layer ofchemical agent on the surface of the blanket that assists the inkdroplets to retain their film-like shape after they have impacted thesurface of the blanket.

While a roller can be used to apply an even film, in an alternativeembodiment the pre-treatment or conditioning material is sprayed ontothe surface of the blanket and optionally spread more evenly, forexample by the application of a jet from an air knife. Independently ofthe method used to apply the conditioning solution, if needed, thelocation at which such pre-print treatment can be performed may bereferred herein as the conditioning station. The alternative printingsystem illustrated in FIG. 3 may also include a conditioning station.

The purpose of the applied chemical agent is to counteract the effect ofthe surface tension of the aqueous ink upon contact with the hydrophobicrelease layer of the blanket, without necessarily reducing said surfacetension. Without wishing to be bound by theory, it is believed that suchpre-treatment chemical agents, for instance some positively chargedpolymers, such as polyethylenimine, will adhere (temporarily at least),to the silicone surface of the transfer member to form a positivelycharged layer. However, the amount of charge that is present in such alayer is believed to be much smaller than the negative charge in thedroplet itself. The present inventors have found that a very thin layerof chemical agent, perhaps even a layer of molecular thickness, isadequate. This layer of pre-treatment chemical agent on the transfermember may be applied in very dilute form of the suitable chemicalagents. Ultimately this thin layer may be transferred onto thesubstrate, along with the image being impressed.

When the ink droplet impinges on the transfer member, the momentum inthe droplet causes it to spread into a relatively flat volume. In theprior art, this flattening of the droplet is almost immediatelycounteracted by the combination of surface tension of the droplet andthe hydrophobic nature of the surface of the transfer member.

In embodiments of the invention, the shape of the ink droplet is“frozen” such that at least some and preferably a major part of theflattening and horizontal extension of the droplet present on impact ispreserved. It should be understood that since the recovery of thedroplet shape after impact is very fast, the methods of the prior artwould not effect phase change by agglomeration and/or coagulation and/ormigration.

Without wishing to be bound by theory, it is believed that, on impact,the positive charges which have been placed on the transfer memberattract the negatively charged polymer resin particles of the inkdroplet that are immediately adjacent to the surface of the member. Itis believed that, as the droplet spreads, this effect takes place alonga sufficient area of the interface between the spread droplet and thetransfer member to retard or prevent the beading of the droplet, atleast on the time scale of the printing process, which is generally onthe order of seconds.

As the amount of charge is too small to attract more than a small numberof charged resin particles in the ink, it is believed that theconcentration and distribution of the charged resin particles in thedrop is not substantially changed as a result of contact with thechemical agent on the release layer. Furthermore, since the ink isaqueous, the effects of the positive charge are very local, especiallyin the very short time span needed for freezing the shape of thedroplets.

While the applicants have found that coating the intermediate transfermember with a polymer utilizing a roller is an effective method forfreezing the droplets, it is believed that spraying or otherwisechemically transferring positive charge to the intermediate transfermember is also possible.

Ink

Inks that are suitable for use in conjunction with the treated arerelease layer are, for example, aqueous inkjet inks that contain (i) asolvent comprising water and optionally a co-solvent, (ii) a negativelychargeable polymeric resin (the ink may include a small amount of apH-raising substance to ensure that the polymer is negatively charged),and (iii) at least one colorant. Preferably, water constitutes at least8 wt. % of the ink; the at least one colorant is dispersed or at leastpartly dissolved within the solvent and constitutes at least 1 wt. % ofthe ink; the polymeric resin is dispersed or at least partiallydissolved within the solvent and constitutes 6 to 40 wt. % of the ink;the average molecular weight of the polymeric resin is least 8,000;prior to jetting the ink has at least one of (i) a viscosity of 2 to 25centipoise at at least one temperature in the range of 20-60° C. and(ii) a surface tension of not more than 50 milliNewton/m at at least onetemperature in the range of 20-60° C.

Preferably, the ink is such that, when substantially dried, (a) at atleast one temperature in the range of 90° C. to 195° C., the dried inkhas a first dynamic viscosity in the range of 1,000,000 (1×10⁶) cP to300,000,000 (3×10⁸) cP, and (b) at at least one temperature in the rangeof 50° C. to 85° C., the dried ink has a second dynamic viscosity of atleast 80,000,000 (8×10⁷) cP, wherein the second dynamic viscosityexceeds the first dynamic viscosity; and/or the weight ratio of theresin to the colorant is at least 1:1. The colorant may contain apigment, preferably a nanopigment, for example having an averageparticle size (D₅₀) of not more than 120 nm.

With respect to the ink, “substantially dried” refers to ink that has nomore solvent and other volatile compounds than does a layer of the inkof 1 mm initial thickness after such a layer is dried in an oven for 12hours at 100° C.

As noted, the polymer resins, such as acrylic-based polymers, may benegatively charged at alkaline pH. Consequently, in some embodiments,the polymeric resin has a negative charge at pH 8 or higher; in someembodiments the polymeric resin has a negative charge at pH 9 or higher.Furthermore, the solubility or the dispersability of the polymeric resinin water may be affected by pH. Thus in some embodiments, theformulation comprises a pH-raising compound. Examples of such arediethyl amine, monoethanol amine, and 2-amino-2-methyl propanol. SuchpH-raising compounds, when included in the ink, are generally includedin small amounts, e.g. about 1 wt. % of the formulation and usually notmore than about 2 wt. % of the formulation.

It will also be appreciated that acrylic-based polymers having freecarboxyl groups may be characterized in terms of their charge densityor, equivalently, the acid number, viz. the number of mg of KOH neededto neutralize one g of dry polymer. Thus, in some embodiments, thepolymeric resin has an acid number in the range of 70-144.

As noted, the ink formulation contains at least one colorant. As usedherein in the specification and in the claims section that follows, theterm “colorant” refers to a substance that is considered, or would beconsidered to be, a colorant in the art of printing. The concentrationof the at least one colorant within the ink formulation whensubstantially dry may be at least 2%, at least 3%, at least 4%, at least6%, at least 8%, at least 10%, at least 15%, at least 20%, or at least22%, by weight. Typically, the concentration of the at least onecolorant within the ink film is at most 40%, at most 35%, at most 30%,or at most 25%. More typically, the ink formulation when substantiallydry may contain 2-30%, 3-25%, or 4-25% of the at least one colorant. Thecolorant may include at least one pigment. Alternatively oradditionally, the colorant may include at least one dye.

As used herein in the specification and in the claims section thatfollows, the term “pigment” refers to a finely divided solid colorant.The pigment may have an organic and/or inorganic composition. Typically,pigments are insoluble in, and essentially physically and chemicallyunaffected by, the vehicle or medium in which they are incorporated.Pigments may be colored, fluorescent, or pearlescent. Pigments may alterappearance by selective absorption, interference and/or scattering oflight. They are usually incorporated by dispersion in a variety ofsystems and may retain their crystal or particulate nature throughoutthe pigmentation process.

As used herein in the specification and in the claims section thatfollows, the term “dye” refers to at least one colored substance that issoluble or goes into solution during the application process and impartscolor by selective absorption of light.

As used herein in the specification and in the claims section thatfollows, the term “average particle size”, or “D₅₀”, with reference tothe particle size of pigments, refers to an average particle size, byweight, as determined by a laser diffraction particle size analyzer(e.g., Mastersizer™ 2000 of Malvern Instruments, England), usingstandard practice.

A variety of pigments are suitable for use in the inks in accordancewith embodiments of the invention, although it has been found thatresults are best when the average particle size (D₅₀) of the pigment isfrom 10 nm to 300 nm, such as 120 nm or less, for example on the orderof 70-80 nm. The pigments may thus be nanopigments; the particle size ofthe nanopigments may depend on the type of pigment and on the sizereduction methods used in the preparation of the pigments. For example,the particle size for magenta and yellow pigments may be in the range of10 nm to 100 nm, while blue or green pigments may be in the range of 75nm to 200 nm. Generally the D₅₀ of the pigment particles may be within arange of 10 nm to 270 nm. Pigments of various particle sizes, utilizedto give different colors, may be used for the same print. Some pigmentshaving such particle sizes are commercially available, and may beemployed as-is in embodiments of the invention; in other cases, thepigments may be milled to the appropriate size. It will be appreciatedthat in general, the pigments are dispersed (or at least partlydissolved) within the solvent along with the polymeric resin, and notfirst dispersed within the polymeric resin by kneading) to obtaincolored resin particles which are then mixed with the solvent.

In some applications, particularly when it is desirable to have anultra-thin ink film laminated onto the printing substrate, the weightratio of the polymeric resin to the colorant may be at most 7:1, at most5:1, at most 3:1, at most 2.5:1, at most 2:1, or at most 1.7:1.

Examples of suitable co-solvents which are miscible with water areethylene glycol, diethylene glycol, propylene glycol, glycerol, andN-methyl pyrrolidone. Another example is polyethylene glycol 400 (PEG400), although in some embodiments, the ink formulation is substantiallyfree of water soluble polymers. In some embodiments the ink formulationis substantially free of saccharides. The co-solvent may be present as amixture of co-solvents.

In some embodiments, it may be desirable to include, in addition to thepolymeric resin, colorant, water and co-solvent, a small amount of asurfactant, e.g. 0.5-1.5 wt. % of the ink. In some embodiments, thesurfactant is a non-ionic surfactant.

In some embodiments, the ink formulation is devoid or substantiallydevoid of wax. Typically, the ink formulation contains less than 30 wt.% wax, less than 20 wt. % wax, less than 15 wt. % wax, less than 10 wt.% wax, less than 7 wt. % wax, less than 5 wt. % wax, less than 3 wt. %wax, less than 2 wt. % wax, or less than 1 wt. % wax. In otherembodiments, wax is included in the ink formulation in order to impartgreater abrasion resistance in the printed ink. Such waxes may benatural or synthetic, e.g. based on esters of fatty acids and fattyalcohols or long-chain alkanes (paraffin waxes), or mixtures thereof. Insuch cases, the formulation may comprise for example 0.1-10 wt. % wax,e.g. up to 0.1, 0.2, 0.3, 0.4, 0,5, 0.6, 0.7. 0.8, 0.9, 1.0, 1.5, 2,2.5, 3, 4, 5, 6, 7, 8, 9 or 10 wt. % wax. The wax may be incorporatedinto the formulation as an aqueous dispersion of small wax particles,e.g. having average size of 10 micron or smaller, preferably havingaverage size of 1 micron or smaller.

In some erribodiments, the ink formulation is devoid or substantiallydevoid of oils such as mineral oils and vegetable oils (e.g., linseedoil and soybean oil). Typically, the ink formulation contains at most 20wt. %, at most 12 wt. %, at most 8 wt. %, at most 5 wt. %, at most 3 wt.%, at most 1 wt. %, at most 0.5 wt. %, or at most 0.1 wt. %, by weight,of one or more oils, cross-linked fatty acids, or fatty acid derivativesproduced upon air-drying. In some embodiments, the formulation issubstantially free of a. plasticizer.

In some embodiments, the ink formulation is devoid or substantiallydevoid of one or more salts, including salts used to coagulate orprecipitate ink on a transfer member or on a substrate (e.g., calciumchloride). Typically, the ink formulation contains at most 8 wt. %, atmost 5 wt. %, at most 3 wt. %. at most 1 wt. %, at most 0.5 wt. %, atmost 0.1 wt. %, or substantially 0 wt. % of one or more salts. Suchsalts may be referred to herein as “precipitants”, and it will beappreciated that when it is stated that a formulation does not include asalt or contains salt in an amount less than a certain weightpercentage, this does not refer to salts that may form between thepolymer(s) of the polymeric resin and pH modifiers, such as alcoholamines, or that may be present in the polymeric resin itself if thepolymeric resin is provided as a salt. As discussed above, it ispresently believed that the presence of negative charges in thepolymeric resin is beneficial to the print process.

In some embodiments, the ink formulation is devoid or substantiallydevoid of inorganic particulates, e.g. silica particulates, titaniaparticulate or alumina particulates, containing less than 2 wt. %, lessthan 1 wt. %, less than 0.1 wt. % or substantially no inorganicparticulates. By “silica particulates” is meant fumed silica, silicachips, silica. colloids, and the like. Specific examples of such silicaparticulates include those available from DuPont Company under thenames: Ludox AM-30, Ludox CL, Ludox HS-30; and those available fromNya.col Nanotechnologies Company under the names: NexSil 12, NexSil 20,NexSil 8, Nexsil 20, Nexsil 85. In the context of the presentapplication, the term “silica particulates” does not include colorants.

Ink Image Heating

The heaters, either inserted into the support plates 130 or positionedabove the blanket as intermediate drying system 224 and drying station214, are used to heat the blanket to a temperature that is appropriatefor the rapid evaporation of the ink carrier and compatible with thecomposition of the blanket. For blankets comprising for instancesilanol-, modified or terminated polydialkylsiloxane silicones in therelease layer, heating is typically of the order of 150° C., though thistemperature may vary within a range from 700° C. to 180° C. depending onvarious factors such as the composition of the inks and/or of theconditioning solutions if needed. When using beneath heating of thetransfer member, it is desirable for the blanket to have relatively highthermal capacity and low thermal conductivity, so that the temperatureof the body of the blanket 102 will not change significantly as it movesbetween the pre-treatment or conditioning station, the image formingstation and the impression station(s). When using top heating of thetransfer member, the blanket would preferably include a thermallyinsulating layer to prevent undue dissipation of the applied heat. Toapply heat at different rates to the ink image carried by the transfersurface, independently of the architecture of a particular printingsystem, additional external heaters or energy sources (not shown) may beused to apply energy locally, for example prior to reaching theimpression stations to render the ink residue tacky (see 231 in FIG. 3),prior to the image forming station to dry the conditioning agent ifnecessary and at the printing station to start evaporating the carrierfrom the ink droplets as soon as possible after they impact the surfaceof the blanket.

The external heaters may be, for example, hot gas or air blowers 306 (asrepresented schematically in FIG. 1) or radiant heaters focusing, forexample, infrared radiation onto the surface of the blanket, which mayattain temperatures in excess of 175° C., 190° C., 200° C., 210° C., oreven 220° C.

The residue film left behind in embodiments of the invention may have anaverage thickness below 1500 nm, below 1200 nm, below 1000 nm, below 800nm below 600 nm, below 500 nm, below 400 nm, or below 300 nm.

As explained above, temperature control is of paramount importance tothe printing system if printed images of high quality are to beachieved. This is considerably simplified in the embodiment of FIG. 3 inthat the thermal capacity of the belt is much lower than that of theblanket 102 in the embodiments of FIGS. 1 and 2.

It has also been proposed above in relation to the embodiment using athick blanket 102 to include additional layers affecting the thermalcapacity of the blanket in view of the blanket being heated frombeneath. The separation of the belt 210 from the blanket 219 in theembodiment of FIG. 3 allows the temperature of the ink droplets to bedried and heated to the softening temperature of the resin using muchless energy in the drying section 214. Furthermore, the belt may cooldown before it returns to the image forming station which reduces oravoids problems caused by trying to spray ink droplets on a hot surfacerunning very close to the inkjet nozzles. Alternatively andadditionally, a cooling station may be added to the printing system toreduce the temperature of the belt to a desired value before the beltenters the image forming station. Cooling may be effected by passing thebelt 210 over a roller of which the lower half is immersed in a coolant,which may be water or a cleaning/treatment solution, by spraying acoolant onto the belt of by passing the belt 210 over a coolantfountain.

In some of the arrangements discussed hitherto, the release layer of thebelt 210 has hydrophobic properties to ensure that the tacky ink residueimage peels away from it cleanly in the transfer station. However, atthe image forming station the same hydrophobic properties areundesirable because aqueous ink droplets can move around on ahydrophobic surface and, instead of flattening on impact to formdroplets having a diameter that increases with the mass of ink in eachdroplet, the ink tends to ball up into spherical globules. As discussed,in structures using a hydrophobic release layer, steps therefore need tobe taken to encourage the ink droplets, which flatten out into a disc onimpact, to retain their flattened shape during the drying and transferstages.

Printing systems as described herein may be produced by modification toexisting lithographic printing presses. The ability to adapt existingequipment, while retaining much of the hardware already present,considerably reduces the investment required to convert from technologyin common current use. In particular, in the case of the embodiment ofFIG. 1, the modification of a tower would involve replacement of theplate cylinder by a set of print bars and replacement of the blanketcylinder by an image transfer drum having a hydrophobic outer surface orcarrying a suitable blanket. In the case of the embodiment of FIG. 3,the plate cylinder would be replaced by a set of print bars and a beltpassing between the existing plate and blanket cylinders. The substratehandling system would require little modification, if any. Colorprinting presses are usually formed of several towers and it is possibleto convert all or only some of the towers to digital printing towers.Various configurations are possible offering different advantages. Forexample each of two consecutive towers may be configured as a multicolordigital printer to allow duplex printing if a perfecting cylinder isdisposed between them. Alternatively, multiple print bars of the samecolor may be provided on one tower to allow an increased speed of theentire press.

The following examples illustrate inkjet ink formulations in accordancewith embodiments of the invention, and in some cases their performancein a printing method as described above.

A general procedure for preparing inks in accordance with embodiments ofthe invention is as follows: first, a pigment concentrate is prepared bymixing distilled water, at least a portion of the polymeric resin ordispersant, if used, and colorant, and milling until a suitable particlesize is reached; if a pH-raising compound is used it may be included inthis step. Thereafter, the remaining ingredients, including additionalpolymeric resin, are mixed in, and then the ink is filtered.

EXAMPLE 1

An inkjet ink formulation was prepared containing:

Ingredient Function wt. % Jet Magenta DMQ (BASF) pigment 2 Joncryl HPD296 (BASF) polymeric resin (acrylic 10.6** (solid styrene co-polymersolu- resin content) tion, ave. MW ~11,500) Glycerol (Aldrich)Water-miscible co-solvent 20 BYK 345 (BYK) surfactant (silicone) 0.5Water — Balance to 100% **The polymeric resin was provided in a 35.5 wt.% water solution; 30 wt. % of the final formulation consisted of thissolution, i.e. 10.6 wt. % in the final ink formulation consisted of thepolymeric resin itself.

To prepare this ink formulation, a pigment concentrate containingpigment (10%), water (70%) and resin—in the present case Joncryl HPD296—(20%) was made by mixing and milling them until the particle size(D₅₀) reached about 70 nm, The remaining materials were then added tothe pigment concentrate and mixed, After mixing, the ink was filteredthrough a 0.5 micron filter. At 25° C., the viscosity of the ink thusobtained was about 9 cP, and the surface tension was approximately 25mN/m.

EXAMPLES 2A and 2B

An inkjet ink formulation was prepared containing:

Ingredient Function wt. % PV Fast Blue BG (Clariant) Pigment 2.3 NeocrylBT-9 (40% water polymeric resin (acrylic 16.5 (6.6 dispersion) (DSMresins) polymer, average solid resin)** MW ~68,000) Glycerol (Aldrich)Water-miscible co-solvent 3.3 Capstone FS-65 (DuPont) Non-ionicfluorosurfactant 0.1 Water — Balance to 100% Joncryl HPD 296 (35.5%Dispersant 9 (3.2 water solution) (BASF) solid resin)** Diethyleneglycol(Aldrich) Water-miscible co-solvent 20 Diethyl amine (Aldrich) pH raiser1 **The BT-9 resin was provided in a 40 wt. % water dispersion, the HPD296 was provided in a 35.5 wt. % water solution. 16.5% and 9%,respectively, of the final formulation consisted of these twocomponents, i.e. 6.6 wt. % of the final ink formulation consisted ofBT-9 itself and 3.2 wt. % consisted of HPD 296 itself.

Another inkjet ink formulation was prepared containing:

Ingredient Function wt. % PV Fast Blue BG (Clariant) Pigment 2.3 NeocrylBT-9 (40% water polymeric resin (acrylic 17.25 (6.9 dispersion) (DSMresins) polymer, average solid resin)** MW ~68,000) Glycerol (Aldrich)Water-miscible co-solvent 3.3 Capstone FS-65 (DuPont) Non-ionicfluorosurfactant 0.1 Water — Balance to 100% Joncryl HPD 296 (35.5%Dispersant 9 (3.2 water solution) (BASF) solid resin)** Diethyleneglycol(Aldrich) Water-miscible co-solvent 20 Diethyl amine (Aldrich) pH raiser1 **The BT-9 resin was provided in a 40 wt. % water dispersion, the HPD296 was provided in a 35.5 wt. % water solution. 17.25% and 9%,respectively, of the final formulation consisted of these twocomponents, i.e. 6.9 wt. % of the final ink formulation consisted ofBT-9 itself and 3.2 wt. % consisted of HPD 296 itself.

To prepare these formulations, pigment concentrates containing pigment(14%), water (79%) and Joncryl HPD 296 (7%) was prepared by mixing theseingredients and milling them until the particle size (D₅₀) reached 70nm, as described in Example 1. Then the remaining materials were addedto the pigment concentrate and mixed. After mixing the inks werefiltered through 0.5 micron filter. At 25° C., the viscosity of the inksthus obtained was about 13 cP, the surface tension about 27 mN/m, andthe pH was 9-10.

EXAMPLES 3A and 3B

An inkjet ink formulation was prepared containing:

Ingredient Function wt. % Jet Magenta DMQ (BASF) Pigment 2.3 NeocrylBT-26 (40% water polymeric resin (acrylic 17.25 (6.9 dispersion) (DSMresins) polymer, ave. MW 25,000) solid resin)** Monoethanol amine pHraiser 1.5 Propylene glycol Water-miscible co-solvent 20N-methylpyrrolidone Water-miscible co-solvent 10 BYK 349 (BYK)surfactant (silicone) 0.5 Water — Balance to 100% **The polymeric resinwas provided in a 40 wt. % water dispersion; the final ink formulationconsisted of 17.25 wt. % of this dispersion, i.e. 6.9 wt. % in the finalink formulation consisted of the polymeric resin itself.

Another inkjet ink formulation was prepared containing:

Ingredient Function wt. % Jet Magenta DMQ (BASF) Pigment 2.3 NeocrylBT-26 (40% water polymeric resin (acrylic 17.5 (7 dispersion) (DSMresins) polymer, ave. MW 25,000) solid resin)** Monoethanol amine pHraiser 1.5 Propylene glycol Water-miscible co-solvent 20N-methylpyrrolidone Water-miscible co-solvent 10 BYK 349 (BYK)surfactant (silicone) 0.5 Water — Balance to 100% **The polymeric resinwas provided in a 40 wt. % water dispersion; the final ink formulationconsisted of 17.5 wt. % of this dispersion, i.e. 7 wt. % in the finalink formulation consisted of the polymeric resin itself.

To prepare these ink formulations, first a pigment concentrate was madeby mixing the pigment (10%), water (69%), Neocryl BT-26 (20%) andmonoethanolamine (1%) and milling as described in Example 1 until theparticle size (D₅₀) reached 70 nm. Then the rest of materials were addedto the pigment concentrate and mixed. After mixing the ink was filteredthrough a 0.5 micron filter. At 25° C., the viscosity of the ink thusobtained was about 8 cP, the surface tension was approximately 24 mN/m,and the pH was 9-10.

EXAMPLE 4

An inkjet ink formulation was prepared containing:

Ingredient Function wt. % Jet Magenta DMQ (BASF) Pigment 2.2 Joncryl 683neutralized Dispersant (styrene acrylic 0.6 with KOH (BASF) copolymer,MW ~8000) Neocryl BT-9 (40% water polymeric resin (acrylic 25 (10dispersion) (DSM resins) polymer, average solid resin)** MW ~68,000)Ethylene glycol Water-miscible co-solvent 25 Propylene glycolWater-miscible co-solvent 10 PEG 400 Water-miscible co-solvent 2Glycerol Water-miscible co-solvent 3 BYK 349 (BYK) surfactant (silicone)0.5 Water — Balance to 100% **The polymeric resin was provided in a 40wt. % water dispersion; the final ink formulation consisted of 25 wt. %of this dispersion, i.e. 10 wt. % of the final ink formulation waspolymeric resin itself.

A pigment concentrate was formed by mixing the pigment (12.3%), water(84.4%) and Joncryl 683 fully neutralized with KOH (3.3%) and milling asdescribed in Example 1 until the particle size (D₅₀) reached 70 nm. Thenthe rest of materials were added to the pigment concentrate and mixed.After mixing the ink was filtered through a 0.5 micron filter. At 25°C., the viscosity of the ink thus obtained was about 7 cP, the surfacetension was approximately 24 mN/m, and the pH was 7-8.

EXAMPLE 5

An inkjet ink formulation was prepared containing:

Ingredient Function wt. % Carbon Black Mogul L Pigment 2.2 (Cabot)Joncryl HPD 671 neutral- Dispersant 0.6 ized with KOH (BASF) NeoRadR-440 (40% water polymeric resin (aliphatic 30 (12 emulsion) (DSMresins) polyurethane, MW 25,000) solid resin)** Propylene glycolWater-miscible co-solvent 40 2-Amino-2-Methyl-1- pH raiser 1 PropanolGlycerol Water-miscible co-solvent 5 BYK 349 (BYK) surfactant (silicone)0.5 Water — Balance to 100% **The polymeric resin was provided in a 40wt. % water emulsion; the final ink formulation consisted of 30 wt. % ofthis emulsion, i.e. 12 wt. % in the final ink formulation was polymericresin itself.

A pigment concentrate was formed by mixing the pigment (14.6%), water(81.5%) and Joncryl 671 fully neutralized with KOH (3.9%) and milling asdescribed in Example 1 until the particle size (D₅₀) reached 70 nm. Thenthe rest of materials were added to the pigment concentrate and mixed.After mixing the ink was filtered through a 0.5 micron filter. At 25°C., the viscosity of the ink thus obtained was about 10 cP, the surfacetension was approximately 26 mN/m, and the pH was 9-10.

EXAMPLE 6

In a manner similar to those described in the preceding examples, aninkjet ink formulation was prepared containing:

Ingredient Function wt. % Hostajet Black O-PT Pigment 2.4 (Clariant)Neocryl BT-26 (40% water polymeric resin (acrylic 7.2** dispersion) (DSMresins) polymer, ave. MW 25,000) monoethanolamine pH raiser 1.5Propylene glycol Water-miscible co-solvent 20 N-methylpyrrolidoneWater-miscible co-solvent 10 BYK 349 (BYK) surfactant (silicone) 0.5Water — Balance to 100% **The polymeric resin was provided in a 40 wt. %water dispersion; this dispersion constitute 18% of the final product,so that the 7.2 wt. % in the final ink formulation refers to theconcentration of the polymeric resin itself, without water.

The above-provided formulation contains approximately 9.6% ink solids,of which 25% (2,4% of the total formulation) is pigment, and about 75%(40%*18%=7.2% of the total formulation) is resin, by weight.

EXAMPLE 7

In a manner similar to those described in the preceding examples, aninkjet ink formulation was prepared containing:

Ingredient Function wt. % Duasyn Red 3B-SF liquid Dye 4 (Clariant)Joncryl HPD 296 (35.5% polymeric resin (acrylic 20 (7.1 sol'n in water)(BASF) styrene co-polymer solu- solid resin)** tion, ave. MW ~11,500)Diethylene glycol Water-miscible co-solvent 20 N-methylpyrrolidoneWater-miscible co-solvent 10 BYK 333 (BYK) surfactant (silicone) 0.5Water — Balance to 100% **The polymeric resin was provided in a 35.5 wt.% water solution; this solution constitutes 20% of the final product, sothat the 7.1 wt. % in the final ink formulation refers to theconcentration of the polymeric resin itself.

EXAMPLE 8

An inkjet ink formulation was prepared containing:

Ingredient Function wt. % Carbon Black Mogul L Pigment 1.3 (Cabot)Joncryl HPD 296 35.5% polymeric resin (acrylic 12.5** water solution(BASF) styrene copolymer solution, ave. MW ~11,500) Diethanolamine pHraiser 1 Glycerol Water-miscible co-solvent 15 Zonyl FSO-100 (DuPont)fluorosurfactant 0.2 Water — Balance to 100% **The polymeric resin wasprovided in a 35.5 wt. % water solution; the 12.5 wt. % in the final inkformulation refers to the concentration of the polymeric resin itself.

A pigment concentrate was formed by mixing the pigment (14 wt. %),Joncryl FLPD 296 (7 wt. % solids), and water (79 wt. %, tripledistilled) and milling until the particle size (D₅₀) reached 70 nm. Thenthe rest of materials were then added to the pigment concentrate andmixed. After mixing the ink was filtered through a 0.5 micron filter. At25° C., the viscosity of the ink thus obtained was about 9 cP and thesurface tension was approximately 24 mN/m.

EXAMPLE 9

An inkjet ink formulation may be prepared containing:

Ingredient Function wt. % Carbon Black Mogul L Pigment 2.2 (Cabot)Disperbyk-198 (BYK- Dispersant 1.4 Chemie GmbH) Joncryl 142E (40% waterpolymeric resin (acrylic 15 (6 dispersion) (DSM resins) polymer, ave. MW40,000) solid resin)** Propylene glycol Water-miscible co-solvent 15Ammonia (25% water pH raiser 2.4 (0.6 sol'n) ammonia) GlycerolWater-miscible co-solvent 5 BYK 349 (BYK) surfactant (silicone) 0.5Water — Balance to 100% **The polymeric resin was provided in a 40 wt. %water emulsion; this constitutes 17.5 wt. % of the final inkformulation, i.e. 7 wt. % in the final ink formulation is 142E resinitself.

A pigment concentrate is formed. by mixing the pigment (10 wt. %), water(83.6 wt. %) and Disperbyk-198 (6.4 wt. %) and milling. The progress ofmilling is controlled on the basis of particle size measurement(Malvern, Nanosizer). The milling is stopped when the particle size(D₅₀) reaches 70 nm. Then the rest of materials are added to the pigmentconcentrate and mixed. After mixing, the ink is filtered through a 0.5micron filter. At 25° C., the viscosity of the ink thus obtained wasabout 15 cP, the surface tension was approximately 26 mN/m, and the pHwas 9-10.

EXAMPLE 10

An inkiet ink formulation may be prepared containing:

Ingredient Function wt. % PV Fast Blue BG (Clariant) Pigment 2.3 NeocrylBT-9 (40% water Polymeric Resin (acrylic 17.5 (7 dispersion) (DSMresins) polymer dispersion, ave. solid resin)** MW ~68,000) Glycerol(Aldrich) Water-miscible co-solvent 3.3 Capstone FS-65 (DuPont)Non-ionic fluorosurfactant 0.1 Water — Balance to 100% EFKA 4580 (BASF)Dispersant 1.8 Diethyleneglycol (Aldrich) Water-miscible co-solvent 20Diethyl amine (Aldrich) pH raiser 1 **The polymeric resin was providedin a 40 wt. % water emulsion; this constitutes 17.5 wt. % of the finalink formulation, i.e. 7 wt. % in the final ink formulation is BT-9 resinitself.

A pigment concentrate is formed h mixing the pigment (10 wt. %), water(87.6 wt. %) and EFKA 4580 (5.5 wt. %) and milling. The progress ofmilling is controlled on the basis of particle size measurement(Malvern, Nanosizer). The milling is stopped when the particle size(D₅₀) reaches 70 nm. Then the rest of materials are added to the pigmentconcentrate and mixed. After mixing, the ink is filtered through a 0.5micron filter. At 25° C., the viscosity of the ink thus obtained wasabout 9 cP, the surface tension was approximately 24 mN/m, and the pHwas 9-10.

Formulations similar to those of Examples 9 and 10 may be prepared usingEFKA® 4560, EFKA® 4585, EFKA® 7702 or Lumitee N—OC 30 as the dispersant.

EXAMPLE 11

An inkjet ink formulation was prepared containing:

Ingredient Function wt. % Jet Magent DMQ Pigment 2 Neocryl BT-102 (40%Polymeric Resin (acrylic 20 (8 water dispersion) polymer) solid resin)**(DSM resins) Propylene Glycol (Aldrich) Water-miscible co-solvent 20 Byk348 Non-ionic fluorosurfactant 0.2 Disperbyk 198 Dispersant 2 Water —Balance to 100% **The polymeric resin was provided in a 40 wt. % wateremulsion; this constituted 20 wt. % of the final ink formulation, i.e. 8wt. % in the final ink formulation was BT-102 resin itself.

Preparation: a pigment concentrate was formed by mixing pigment (14 wt.% water (72 wt. %) and Disperbyk 198 (14 wt. %) and milling. Theprogress of milling was controlled on the basis of particle sizemeasurements (Malvern, Nanosizer). The milling was stopped when theaverage particle size (D₅₀) reached 70 nm. The remaining materials werethen added to the pigment concentrate and mixed. After mixing, the inkwas filtered through a 0.5 μm filter. At 25° C., the viscosity of theink thus obtained was about 5.5 cP, the surface tension was about 25mN/m, and the pH was 6.5.

EXAMPLE 12

In a manner similar to those described in the preceding examples, aninkjet ink formulation was prepared containing:

Ingredient Function wt. % Basonyl Blue 636 (BASF) Water soluble dye 1Joncryl 142E (40% water polymeric resin (acrylic 10 (4% of dispersion)(BASF) polymer, ave. MW 40,000) solid resin) monoethanolamine pH raiser1.5 Propylene glycol Water-miscible co-solvent 20 N-methylpyrrolidoneWater-miscible co-solvent 10 BYK 348 (BYK) surfactant (silicone) 0.5Water — Balance to 100% **The polymeric resin was provided in a 40 wt. %water dispersion; this dispersion constituted 10% of the final product,i.e. 4 wt. % of the final ink formulation was Joncryl 142E resin per se.

EXAMPLE 13

In a manner similar to those described in the preceding examples, aninkjet ink

Ingredient Function wt. % Heliogen Blue D Water soluble dye 1 7086(BASF) Joncryl 537-E (46.5% polymeric resin 15 (7% of water dispersion)(BASF) (acrylic polymer, solid resin) ave. MW >200,000) Disperbyk 198(BYK) Dispersant 3.5 ethylene glycol Water-miscible co-solvent 25Glycerol Water-miscible co-solvent 5 BYK 349 (BYK) surfactant (silicone)0.1 Water — Balance to 100% **The polymeric resin was provided in a 46.5wt. % water dispersion; this dispersion constituted 15% of the finalproduct, i.e. 7 wt. % of the final ink formulation was Joncryl 537Eresin per se.

A pigment concentrate was prepared by mixing pigment (10%), water(72.5%) and Disperbyk 198 (17.5%) and milling until the average particlesize (d50) reached 70 nm.

The remaining materials were then added to the pigment concentrate andmixed. After mixing, the ink was filtered through a 0.5 μm filter. At25° C., the viscosity of the ink thus obtained was about 7.5 cP, thesurface tension about 27 triN/m, and the pH was 8-9.

With respect to the foregoing examples, various milling procedures andapparati will be apparent to those of ordinary skill in the art. Variouscommercially available nano-pigments may be used in the inventive inkformulations. These include pigment preparations such as HostajetMagenta. ESB-PT and Hostajet Black O-PT, both from Clariant, as well aspigments demanding post-dispersion processes, such as Cromophtal JetMagenta DMQ and Irgalite Blue GLO, both from BASF.

One of ordinary skill in the art may readily recognize that variousknown colorants and colorant formulations may be used in the inventiveink or inkjet ink formulations. In some embodiments, such pigments andpigment formulations may include, or consist essentially of, inkjetcolorants and inkjet colorant formulations.

Alternatively or additionally, the colorant may be a dye. Examples ofdyes suitable for use in the ink formulations of the present inventioninclude: Duasyn Yellow 3GF-SF liquid, Duasyn Acid Yellow XX-SF, DuasynRed 3B-SF liquid, Duasynjet Cyan FRL-SF liquid (all manufactured byClariant); Basovit Yellow 133, Fastusol Yellow 30 L, Basacid Red 495,Basacid Red 510 Liquid, Basacid Blue 762 Liquid, Basacid Black X34Liquid, Basacid Black X38 Liquid, Basacid Black X40 Liquid, Basonyl Red485, Basonyl Blue 636 (all manufactured by BASF).

It will also be appreciated that it is possible to formulate an inkconcentrate. This is similar to the procedure described above, differingin that, after forming the pigment (or dye) concentrate, the remainingingredients are added and mixed, except that most or all of theadditional solvent (water and co-solvent) is not added. The additionalsolvent may be mixed into such a concentrate at a later time, forexample after the concentrate has been shipped to an end-user, to yieldan inkjet ink formulation in accordance with embodiments of theinvention. The concentrate may be diluted by addition of, for example,at least 50%, at least 100%, at least 150%. at least 200%, at least250%, at least 300%, least 350% or at least 400% solvent on aweight/weight basis relative to the concentrate to yield the aqueousinkjet ink formulation.

EXAMPLE 14

A piece of transfer blanket having a silanol-terminated polydimethylsiloxane silicone release layer of approximately 200 mm×300 mm was fixedon a hotplate and heated to 130° C. An aqueous solution containing 0.2wt. % of tested pretreatment material was applied to the release layerto a thickness of 1 micron to completely cover the silicone releaselayer. In cases in which the material was supplied as a solution, e.g.40 wt. % PEI in water, the solution was diluted in accordance with thesupplier's stated concentration. This was allowed to dry to leave a thin(˜1 nm thick) layer of the material. Then the entire surface was printedwith drops of ink of 10 picoliter drop size, using aqueous nano-pigmentcyan ink described above and a Fujifilm Dimatix DMP-2800 printer(http://www.fujifilmusa.com/products/industrial_inkjet_printheads/deposition-products/dmp-2800/index. ht m1). This was also allowed to dry andthe ink residue image was then transferred to Condat Gloss® 135 gsmpaper at 130° C. by wrapping the paper around a cylinder and pressingthe cylinder into the release layer as the cylinder was rolled over therelease layer. The optical density (O.D.) of the ink on the paper wasthen measured using an X-rite 528 spectrodensitometerwww.xrite.com/product_overview.aspx?id=14). As a control, this sameprocedure was used, but without first applying a chemical agent to therelease layer. The results are summarized in Table 1. (The difference inresults for Lupasol G20 and Lupasol G20 Waterfree may be attributed tothe higher concentration of chemical agent in the latter.)

TABLE 1 Charge Density, Molecular Chemical Agent [Brand name] meq/gWeight O.D. Control 0.53 Polyethyleneimine (PEI) [Lupasol ® FG] 16 8000.84 PEI [Lupasol ® G 100] 17 5,000 1.1 PEI [Lupasol ® G 20] 16 1,3000.75 PEI [Lupasol ® G 20 Waterfree] 16 1,300 0.92 PEI [Lupasol ® G 35]16 2,000 0.94 PEI [Lupasol ® HF] 17 25,000 1.24 PEI [Lupasol ® P] 20750,000 1.24 PEI, modified [Lupasol ® PN 50] 1,000,000 1.21 PEI,modified [Lupasol ® PN 60] n/a 0.68 PEI, modified [Lupasol ® PO 100]2,000 1.09 PEI [Lupasol ® PR 8515] 16 2,000 0.95 PEI [Lupasol ® PS] 20750,000 1.28 PEI, modified [Lupasol ® SK] 8 2,000,000 1.13 PEI[Lupasol ® WF] 17 25,000 1.28 Poly(diallyldimethylammonium chloride) ~6(calc.) 200,000-300,000 1.2 Poly(4-vinylpyridine) 7 (calc.) 60,000-160,000 Polyallylamine 17.5 (calc.) 17,000 1.17 Chromium,pentahydroxy (tetradecanoato)di- ~6 (calc.) ~500 0.82 [Quilon ™ C9]Chromium, tetrachloro-m-hydroxy[m- ~6 (calc.) ~500 0.77(octadecanoato-O:O′)]di-[Quilon ™ H] chromium complex [Quilon ™ S] 5.5(calc.) 545 0.77 chromium(3+) chloride hydroxide tetradecanoate 6.1(calc.) 490 0.76 (2:4:1:1) [Quilon ™ M] chromium complex [Quilon ™ L] ~6(calc.) ~500 0.75 Hydrogenated tallowalkyl(2-ethylhexyl) dimethyl 0.5quaternary ammonium sulphate [ACER11S08] Quaternary ammonium compounds[ACER11S07] 0.56 C12-C16 alkylbenzyldimethylammonium chloride 0.56[ACER11S15] Tallow dimethyl benzyl ammonium chloride 0.8 [ACER11S16]Oleyltrimethylammonium hexanoate [ACER11S17] 0.52 Oleyltrimethylammoniumdecanoate [ACER11S18] 0.77 Oleyltrimethylammonium oleate [ACER11S19]0.79 Calcium chloride 18 (calc.) 110 0.58 Didecyl dimethyl ammoniumchloride [Arquad 2-10- 2.8 (calc.) 362.08 0.63 80] Didecyl dimethylammonium chloride [Arquad 2.10- 2.8 (calc.) 362.08 0.69 70 HFP]N-Benzyl-N,N-dimethyltetradecan-1-aminium 2.7 (calc.) 368 0.52 chloride[Arquad HTB-75] quaternary ammonium compounds, dicoco 2.2. (calc.) 4470.71 alkyldimethyl, chlorides [Arquad 2C-75] 1-Hexadecanaminium,N,N,N-trimethyl-, chloride 3.1 (calc.) 320 0.64 Arquad 16-50] CocoAlkyltrimethylammonium Chloride [Arquad C- 2.5-3.3 (calc.) 300-400 0.735] dihydrogenated tallow dimethyl ammonium chloride 1.7 (calc.) 5870.61 [Arquad HC-pastilles] ditallowdimethylammonium chloride [Arquad 2T-2-2.5 (calc.) 400-500 0.7 70] Tallowtrimethylammonium chloride [ArquadT-50- n/a n/a 0.63 HFP] Arquad MLB-80 0.59

EXAMPLE 15

When, prior to printing, the outer surface of the image transfer member(the release layer) is treated with a chemical agent that is, orcontains, PEI, transfer of the printed image to a substrate may resultin at least some PEI being transferred as well. The PEI may be detectedusing X-ray photoelectron spectroscopy (XPS) or by other means that willbe known to those of ordinary skill in the art of polymer analysis orchemical analysis of polymers.

Thus, two printed paper substrates were prepared under identicalconditions inkjetting aqueous inkjet ink having nanopigment particlesonto a transfer member, drying the ink and transferring to thesubstrate), except that one was prepared without pretreatment of thetransfer member using PEI and the other was prepared using suchpretreatment. XPS analysis of the printed images was conducted using aVG Scientific Sigma Probe and monochromatic Al Kα x-rays at 1486.6 eVhaving a beam size of 400 μm. Survey spectra were recorded with a passenergy of 150 eV. For chemical state identification of nitrogen, highenergy resolution measurements of N1s were performed with a pass energyof 50 eV. The core level binding energies of the different peaks werenormalized by setting the binding energy for the C1s at 285.0 eV.Deconvolution of the observed peaks revealed that the PEI samplecontained a unique peak at about 402 eV, which corresponds to a C—NH₂⁺-group.

Thus, in an embodiment of the invention, there is provided a printed inkimage having an XPS peak at 402.0±0.2 eV.

EXAMPLE 16

The purpose of the experiment was to check the suitability of candidatechemical agents for the treatment of the release layer. Other than PEI,which was supplied as an aqueous solution (Lupasol® PS, BASF) anddiluted 1:100 to a concentration of about 0.3 wt. %, each chemical agent(N-Hance™ BF 17 cationic guar, N-Hance™ CCG 45 cationic guar, N-Hance™FIPCG 1000 cationic guar, N-Hance™ BF 13 cationic guar, N-Hance™ CG 13cationic guar, N-Hance™ 3196 cationic guar, all from Ashland SpecialtyIngredients) was provided as a powder and dissolved in deionized wateron a weight per weight basis to prepare a conditioning solution, whichwas used “as is” without modification of the resulting pH. Eachconditioning solution was manually applied to a release layer surface ofa blanket of approximately 20 cm x 30 cm size, the release layercomprising a silanol-terminated polydimethylsiloxane silicone and beingat a temperature of 150° C. The conditioning solution was applied bymoistening a Statitech 100% polyester cleanroom wiper with the solutionand wiping the release layer surface. The conditioning solution was thenallowed to dry spontaneously on the heated blanket. Thereafter, a blackink a black ink (containing Carbon Black Mogul L (Cabot), 1.3 wt. %,Joncryl HPD 296 35.5% water solution (BASF), 35% (12% solids). glycerol15%, Zonyl FSO-100 (DuPont) 0.2% and balance water) was jetted at aresolution of 600 dpi×600 dpi onto the conditioned release layer whilestill at 150° C., using conventional Kyocera inkjet print heads. It willbe appreciated that during printing the heated release layer was movedrelative to the print heads at a rate of 75 cm/s. The test file printedfor the experiment printed a gradient of ink coverage, from a less tomore dense population of ink dots. The drop size was set to 3 or 4,which corresponds to 13 pl or 18 pl respectively of ink. The ink filmformed was allowed to dry for at least 5 seconds and then while stillhot was transferred to Condat Gloss® 135 gsm paper using manualpressure, using one of two methods, either by the Paper On Blanket (POB)method, or the Roll method. In POB, the sheet of paper was placeddirectly onto the inked blanket, then manual pressure was applied. InRoll, the paper was tightly fixed with tape to a metal cylinder and theink image was transferred to the paper by manually rolling this paper(with pressure) over the inked blanket. Representative printoutsobtained by the POB method are shown in FIG. 4, wherein the areas oflower ink coverage are omitted and in some cases the area of 100%coverage is truncated. The diameters of several ink dots in two of theless dense regions of the printed area (not shown in the Figures),having drop size 3 or 4, as reported in the tables below, were thendetermined using a Lex t Confocal Microscope at X20 magnification. Themeasures were repeated for 5 representative round dots on areas ofadequate conditioner coverage and the results in each area wereaveraged. The diameters of the various dots were compared. Results arepresented in the Tables 2 and 3 below; PEI=polyethylene imine,GHPTC=guar hydroxypropyltrimonium chloride, HGHPTC=hydroxyl guarhydroxypropyltrimonium chloride; viscosities and charge densities are asreported by the manufacturer. A larger diameter suggests retention ofthe spreading of ink on the release layer and good transfer therefrom.

TABLE 2 Results for POB Chemical agent, Ave. diameter, Ave. diameter,wt. % Material Viscosity Charge density drop size 3 drop size 4 None41.4276 50.5252 Lupasol PS 0.3% PEI Very high 46.3056 56.8316 CG 13 0.1%GHPTC High Medium 47.8436 59.0136 CG 13 0.5% GHPTC High Medium 49.636459.0776 BF 13 0.1% GHPTC High Medium 48.6236 56.1832 BF 13 0.5% GHPTCHigh Medium 46.1368 57.2576 3196 0.1% GHPTC High Medium 47.3428 61.17763196 0.5% GHPTC High Medium 48.1552 59.5168 BF 17 0.1% GHPTC High VeryHigh 47.1568 59.1356 BF 17 0.5% GHPTC High Very High 48.4384 59.0272 CCG45 0.1% GHPTC Low Medium 45.2832 56.1232 CCG 45 0.5% GHPTC Low Medium44.7548 56.3320 Hpcg 1000 0.1% HGHPTC Medium Medium 45.9252 56.8428 Hpcg1000 0.5% HGHPTC Medium Medium 45.4280 58.3904

TABLE 3 Results for Roll chemical agent, Ave. diameter, Ave. diameter,wt. % Material Viscosity Charge density drop size 3 drop size 4 LupasolPS 0.3% PEI Very high 43.2656 54.7352 CG 13 0.1% GHPTC High Medium43.0544 54.3544 CG 13 0.5% GHPTC High Medium 48.2376 58.5096 BF 13 0.1%GHPTC High Medium 47.6172 57.9916 BF 13 0.5% GHPTC High Medium 45.440857.0412 3196 0.1% GHPTC High Medium 49.1352 61.2340 3196 0.5% GHPTC HighMedium 47.5316 56.8892 BF 17 0.1% GHPTC High Very High 46.5030 57.5252BF 17 0.5% GHPTC High Very High 48.4056 58.3452 CCG 45 0.1% GHPTC LowMedium 44.2352 57.1564 CCG 45 0.5% GHPTC Low Medium 44.8136 56.2856 Hpcg1000 0.1% HGHPTC Medium Medium 46.6876 57.9184 Hpcg 1000 0.5% HGHPTCMedium Medium 46.1952 58.1752

The optical densities of these prints, in the region of 100% inkcoverage, were also measured, using an X-rite 500 seriesspectrodensitometer using a 0.5 cm optical probe. The results arepresented in Table 4 (numbers are the average of three measurements; thenumbers in parenthesis indicate the OD of the tested agent as a % of ODof Lupasol PS):

TABLE 4 Material OD - POB OD - Roll None 0.34 PEI 2.00 (100%)  1.95(100%) CG 13 0.1% 1.49 (75%) 1.44 (74%) CG 13 0.5% 1.82 (91%) 1.72 (88%)BF 13 0.1% 2.06 (103%) 1.91 (98%) BF 13 0.5% 1.57 (79%) 1.78 (91%) 31960.1% 2.06 (103%)  2.16 (111%) 3196 0.5% 2.10 (105%)  2.01 (103%) BF 170.1% 1.72 (86%) 1.52 (78%) BF 17 0.5% 2.12 (106%) 1.69 (87%) CCG 45 0.1%1.42 (71%) 1.42 (73%) CCG 45 0.5% 1.25 (63%) 1.59 (82%) Hpcg 1000 0.1%2.18 (109%) 1.86 (95%) Hpcg 1000 0.5% 1.88 (94%) 1.72 (88%)

The above-results show that cationic guars are also suitable chemicalagents to serve for the conditioning of release layers of printingblankets in accordance with embodiments of the invention.

EXAMPLE 17

In a manner similar to Example 16, solutions of various chemical agentswere applied to a 10 square cm (cm²) area of a heated blanket having asilanol-terminated polydimethyl-siloxane silicone release layer anddried prior to printing thereon in a gradient pattern with the aqueousink described in Example 8, this time using a Fujifilm Dimatix DMP-2800printer jetting 10 pl droplets (see FIG. 5). Viviprint™ polymers wereobtained from International Specialty Products, Wayne, N.J. USA; and abranched PEI having MW 2,000,000 was obtained from Polysciences, Inc.,Warrington, Pa. To account for the variations that may result fromdifferences in printing head efficiency over time, ink was jettedsimultaneously onto a surface that was treated with both a PEI solution(1% by volume of Lupasol PS corresponding to about 0.3% weight byweight) as reference and with the chemical agent being tested, each inseparate sections or patches of blanket. For a control, the ink wasprinted on the release layer without prior application of a chemicalagent. The ink was then dried and transferred to Condat Gloss® 135 gsmpaper using a metal roller and manual pressure. Examples of theresulting images on the paper are shown in FIGS. 5A-5D. The opticaldensities of these prints in the 100% coverage region were measured. Theresults are shown in Table 5 below, presented in each case in comparisonto the PEI reference print.

TABLE 5 Chemical agent (solution strength, O.D of PEI OD Agent/ wt. %)Chemistry O.D. (1%) ref. ODPEI Viviprint 131 (0.1%) Copolymer of vinylpyrrolidone 0.93 1.33 70% dimethylaminopropyl methacrylamide Viviprint131 (0.5%) Copolymer of vinyl pyrrolidone 1.07 1.28 84%dimethylaminopropyl methacrylamide Viviprint 200 (0.1%) Terpolymer ofvinyl caprolactam, 0.81 1.08 75% dimethylaminopropyl methacryamide,hydroxyethyl methacrylate Viviprint 200 (0.5%) Terpolymer of vinylcaprolactam 0.95 1.05 90% dimethylaminopropyl methacryamide hydroxyethylmethacrylate Viviprint 650 (0.1%) Quaternized vinyl pyrrolidone/ 0.961.25 77% dimethylaminoethyl methacrylate copolymer in water Viviprint650 (0.5%) Quaternized vinyl pyrrolidone/ 0.92 1.08 85%dimethylaminoethyl methacrylate copolymer in water PEI branched (0.1%)Polyethylenimine 0.93 1.04 89% PEI branched (0.5%) Polyethylenimine 0.850.95 89%

The above results show that various amine polymers are suitable for useas chemical agents in accordance with embodiments of the invention.

EXAMPLE 18

This example is similar to Example 17, but the pH of the solution of thechemical agent being tested was varied by addition of 0.1M HCl or 0.1MNaOH, as appropriate, in order to assess whether or not the pH of theconditioning solution affected the interaction of the chemical agentwith the release layer. Except for cationic guar N-Hance™ 3196, theconcentration of which is provided in wt. %, the strength of all otherconditioning solutions corresponds to the dilution in distilled water ofthe respective supplied stock solution. Optical density was measured atthree points in each of the regions of 50% and 100% ink coverage. Theresults are presented in Table 6, again as a percentage relative to thePEI reference; the term “ref” in Table 6 indicates that the solution wastested “as is”, without any pH adjustment.

TABLE 6 O.D (100%) O.D (50%) Chemical Agent pH Dimatix Dimatix PEI (1%)9.5 1.78 0.72 Viviprint 200 (0.1%) 5.25 1.83 0.54 Viviprint 200 (1%) 51.87 0.49 Viviprint 200 (0.5%) ref 5.26 1.78 0.66 Viviprint 200 (0.5%)4.2 1.40 0.64 Viviprint 200 (0.5%) 3 1.78 0.50 Viviprint 200 (0.5%) 6.51.54 0.69 Viviprint 200(0.5%) 8.3 1.82 0.62 Viviprint131 (0.1%) 5 1.480.51 Viviprint 131 (1%) 4 1.50 0.50 Viviprint 650 (0.1%) 5.2 1.51 0.61Viviprint 650 (1%) 4.8 1.62 0.65 N-Hance 3196 (0.5%) ref 9.5 1.96 0.68N-Hance 3196 (0.5%) 11 2.02 0.74 N-Hance 3196 (0.5%) 8 1.98 0.72 N-Hance3196 (0.5%) 6.9 1.94 0.57 N-Hance 3196 (0.5%) 5.5 1.98 0.68

EXAMPLE 19

Tack (or tackiness) may be defined as the property of a material thatenables it to bond with a surface on immediate contact under lightpressure. Tack performance may be highly related to various viscoelasticproperties of the material (polymeric resin, or ink solids). Both theviscous and the elastic properties would appear to be of importance: theviscous properties at least partially characterize the ability of amaterial to spread over a surface and form intimate contact, while theelastic properties at least partially characterize the bond strength ofthe material. These and other thereto-rheological properties are rateand temperature dependent,

By suitable selection of the thereto-rheological characteristics of theresidue film which is formed by jetting an ink in accordance withembodiments of the invention onto a hydrophobic release layer and dryingthe jetted ink, the effect of cooling may be to increase the cohesion ofthe residue film, whereby its cohesion exceeds its adhesion to therelease layer of the intermediate transfer member so that all orsubstantially all of the residue film is separated from the imagetransfer member and impressed as a film onto a substrate. In this way,it is possible to ensure that the residue film is impressed on thesubstrate without significant modification to the area covered by thefilm nor to its thickness.

Viscosity temperature sweeps—ramp and step—were performed using a ThermoScientific HAAKE RheoStress® 6000 rheometer having a TM-PE-P Peltierplate temperature module and a P20 Ti L measuring geometry (spindle).

Samples of dried ink residue having a imm depth in a 2 cm diametermodule were tested. The samples were dried overnight in an oven at anoperating temperature of 100° C. A volume of sample (pellet) wasinserted into the 2 cm diameter module and softened by gentle heating.The sample volume was then reduced to the desired size by lowering thespindle to reduce the sample volume to the desired depth of 1 mm.

In temperature ramp mode, the sample temperature was allowed tostabilize at low temperature (typically 25° C. to 40° C.) before beingramped up to a high temperature (typically 160° C. to 190° C.) at a rateof approximately 0.33° C. per second. Viscosity measurements were takenat intervals of approximately 10 seconds. The sample temperature wasthen allowed to stabilize at high temperature for 120 seconds beforebeing ramped down to low temperature, at a rate of approximately 0.33°C. per second. Again, viscosity measurements were taken at intervals ofapproximately 10 seconds. Oscillation temperature sweeps were performedat a gamma of 0.001 and at a frequency of 0.1 Hz.

FIG. 6 provides ramped-down temperature sweep plots of dynamic viscosityas a function of temperature, for several dried ink formulationssuitable for the ink film construction of the present invention. Afterreaching a maximum temperature of approximately 160° C., and waiting 120seconds, the temperature was ramped down as described.

The lowest viscosity curve is that of a dried residue of an inventiveyellow ink formulation, containing about 2% pigment solids, and producedaccording to the procedure described hereinabove. At about 160° C., therheometer measured a viscosity of about 6.7·10 ⁶ cP. As the temperaturewas ramped down, the viscosity steadily and monotonically increased toabout 6·10⁷ cP at 95° C., and to about 48·10⁷ cP at 58° C.

The intermediate viscosity curve is that of a dried residue of aninventive cyan ink formulation, containing about 2% pigment solids, andproduced according to the procedure described hereinabove. At about 157°C., the rheometer measured a viscosity of about 86·10⁶ cP. As thetemperature was ramped down, the viscosity increased to about 187·10⁶ cPat 94° C., and to about 8·10⁸ cP at 57° C.

The highest viscosity curve is that of a dried residue of an inventiveblack ink formulation, containing about 2% pigment solids, and producedaccording to the procedure described hereinabove. At about 160° C., therheometer measured a viscosity of about 196·10⁶ cP. As the temperaturewas ramped down, the viscosity steadily and monotonically increased toabout 763·10⁶ cP at 95° C., and to about 302·10⁷ cP at 59° C.

FIG. 7 is a ramped-down temperature sweep plot of dynamic viscosity as afunction of temperature, for several dried ink formulations of thepresent invention, vs. several ink residues of prior art inkformulations. The viscosity curves of the prior art formulations arelabeled 1 to 5, and are represented by dashed lines; the viscositycurves of the inventive formulations are labeled A to E, and arerepresented by solid lines. The ink formulations of the presentinvention include the three previously described in conjunction withFIG. 6 (A =black; C=cyan; and E =yellow), and two ink formulations (“B”;“D”) containing about 2%, by weight of solids, of a magenta pigment[Hostajet Magenta E5B-PT (Clariant)], along with about 6% of variousstyrene-acrylic emulsions. The residues of the prior all inks wereprepared from various commercially available inkjet inks, of differentcolors.

A magnified view of the plot of FIG. 7, for viscosities of less than36·10⁸, is provided in FIG. 8. Only the viscosity curves of theinventive formulations A to E, and that of prior-art formulation 5, maybe seen in FIG. 8.

It is evident from the plots, and from the magnitude of the viscosities,that the dried ink residues of the various prior art ink formulationsexhibit no or substantially no flow behavior over the entire measuredrange of temperatures (up to at least 160° C.). The peaks observed atextremely high viscosities in some plots of the prior-art formulationswould appear to have no physical meaning. The lowest measured viscosityfor each of the prior art residue films was within a range of at least135·10⁷ cP to at least 33·10⁸ cP. The lowest value within this range,135·10⁷ cP, is well over 6 times the highest viscosity value of any ofthe residues of the inventive ink formulations, at about 160° C.

Moreover, during the ramp-down phase of the experiment, Samples 1 to 5of the prior art exhibited viscosity values that exceeded the viscositymeasured at about 160° C., and/or appear sufficiently high so as topreclude transfer of the film. In practice, the inventors of the presentinvention successfully transferred all five of the inventive ink filmsto a printing substrate, but failed to transfer any of the fiveprior-art ink films to a printing substrate, even after heating to over160° C.

The present invention has been described using detailed descriptions ofembodiments thereof that are provided by way of example and are notintended to limit the scope of the invention. The described embodimentscomprise different features, not all of which are required in allembodiments of the invention. Some embodiments of the present inventionutilize only some of the features or possible combinations of thefeatures. Variations of embodiments of the present invention that aredescribed and embodiments of the present invention comprising differentcombinations of features noted in the described embodiments will occurto persons skilled in the art to which the invention pertains,

In the description and claims of the present disclosure, each of theverbs, “comprise” “include” and “have”, and conjugates thereof, are usedto indicate that the object or objects of the verb are not necessarily acomplete listing of members, components, elements or parts of thesubject or subjects of the verb. As used herein, the singular form “a”,“an” and “the” include plural references unless the context clearlydictates otherwise. For example, the term “an impression station” or “atleast one impression station” may include a plurality of impressionstations,

1-26. (canceled)
 27. A hydrophobic release layer of an intermediatetransfer member of a printing system having disposed thereupon apolymeric chemical agent having a nitrogen content of at least 1 wt. %and at least one of (a) a nitrogen content of at least 1 wt. %, apositive charge density of at least 3 meq/g of chemical agent and anaverage molecular weight of at least 5,000, (b) a nitrogen content of atleast 1 wt. %, a positive charge density of at least 1 meq/g of chemicalagent and an average molecular weight of at least 1000, (c) a nitrogencontent of at least 1% and an average molecular weight of at least50,000, and (d) a nitrogen content of at least 18% and an averagemolecular weight of at least 10,000.
 28. The release layer of claim 27,wherein the chemical agent has an average molecular weight of at least800, at least 1,000, at least 1,300, at least 1,700, at least 2,000, atleast 2,500, at least 3,000, at least 3,500, at least 4,000, at least4,500, at least 5,000, of at least 10,000, at least 15,000, at least20,000, at least 25,000, at least 50,000, at least 100,000, at least150,000, at least 200,000, at least 250,000, at least 500,000, at least750,000, at least 1,000,000, or at least 2,000,000.
 29. The releaselayer of claim 27 the charge density is at least 6 meq/g of chemicalagent.
 30. The release layer of claim 27 wherein the polymer is selectedfrom the group consisting of linear polyethylene imine, branchedpolyethylene imine, modified polyethylene imine,poly(diallyldimethylammonium chloride), poly(4-vinylpyridine),polyallylamine, a vinyl pyrrolidone-dimethylaminopropyl methacrylamideco-polymer a vinyl caprolactam-dimethylaminopropyl methacryamidehydroxyethyl methacrylate copolymer a quaternized copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate with diethyl sulfate aguar hydroxypropyltrimonium chloride, and a hydroxypropyl guarhydroxypropyltrimonium chloride.
 31. The release layer of claims 27,wherein the concentration of the chemical agent on the release layer isnot more than 50 mg per square meter, not more than 40 mg/m², not morethan 30 mg/m², not more than 20 mg/m², not more than 10 mg/m², not morethan 5 mg/m², not more than 4 mg/m², not more than 3 mg/m², not morethan 2 mg/m², not more than 1 mg/m², not more than 0.5 mg/m², not morethan 0.1 mg/m², not more than 0.05 mg/m², or not more than 0.01 mg/m².32-85. (canceled)
 86. The release layer of claim 28 wherein the chargedensity is at least 6 meq/g of chemical agent.
 87. The release layer ofclaim 28 wherein the polymer is selected from the group consisting oflinear polyethylene imine, branched polyethylene imine, modifiedpolyethylene imine, poly(diallyldimethylammonium chloride),poly(4-vinylpyridine), polyallylamine, a vinylpyrrolidone-dimethylaminopropyl methacrylamide co-polymer, a vinylcaprolactam-dimethylaminopropyl methacryamide hydroxyethyl methacrylatecopolymer, a quaternized copolymer of vinyl pyrrolidone anddimethylaminoethyl methacrylate with diethyl sulfate, a guarhydroxypropyltrimonium chloride, and a hydroxypropyl guarhydroxypropyltrimonium chloride.
 88. The release layer of claim 29wherein the polymer is selected from the group consisting of linearpolyethylene imine, branched polyethylene imine, modified polyethyleneimine, poly(diallyldimethylammonium chloride), poly(4-vinylpyridine),polyallylamine, a vinyl pyrrolidone-dimethylaminopropyl methacrylamideco-polymer, a vinyl caprolactam-dimethylaminopropyl methacryamidehydroxyethyl methacrylate copolymer, a quaternized copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate with diethyl sulfate, aguar hydroxypropyltrimonium chloride, and a hydroxypropyl guarhydroxypropyltrimonium chloride.
 89. The release layer of claim 86wherein the polymer is selected from the group consisting of linearpolyethylene imine, branched polyethylene imine, modified polyethyleneimine, poly(diallyldimethylammonium chloride), poly(4-vinylpyridine),polyallylamine, a vinyl pyrrolidone-dimethylaminopropyl methacrylamideco-polymer, a vinyl caprolactam-dimethylaminopropyl methacryamidehydroxyethyl methacrylate copolymer, a quaternized copolymer of vinylpyrrolidone and dimethylaminoethyl methacrylate with diethyl sulfate, aguar hydroxypropyltrimonium chloride, and a hydroxypropyl guarhydroxypropyltrimonium chloride.
 90. The release layer of claim 28,wherein the concentration of the chemical agent on the release layer isnot more than 50 mg per square meter, not more than 40 mg/m², not morethan 30 mg/m², not more than 20 mg/m², not more than 10 mg/m², not morethan 5 mg/m², not more than 4 mg/m², not more than 3 mg/m², not morethan 2 mg/m², not more than 1 mg/m², not more than 0.5 mg/m², not morethan 0.1 mg/m², not more than 0.05 mg/m², or not more than 0.01 mg/m².91. The release layer of claim 29, wherein the concentration of thechemical agent on the release layer is not more than 50 mg per squaremeter, not more than 40 mg/m², not more than 30 mg/m², not more than 20mg/m², not more than 10 mg/m², not more than 5 mg/m², not more than 4mg/m², not more than 3 mg/m², not more than 2 mg/m², not more than 1mg/m², not more than 0.5 mg/m², not more than 0.1 mg/m², not more than0.05 mg/m², or not more than 0.01 mg/m².
 92. The release layer of claim30, wherein the concentration of the chemical agent on the release layeris not more than 50 mg per square meter, not more than 40 mg/m², notmore than 30 mg/m², not more than 20 mg/m², not more than 10 mg/m², notmore than 5 mg/m², not more than 4 mg/m², not more than 3 mg/m², notmore than 2 mg/m², not more than 1 mg/m², not more than 0.5 mg/m², notmore than 0.1 mg/m², not more than 0.05 mg/m², or not more than 0.01mg/m².
 93. The release layer of claim 86, wherein the concentration ofthe chemical agent on the release layer is not more than 50 mg persquare meter, not more than 40 mg/m², not more than 30 mg/m², not morethan 20 mg/m², not more than 10 mg/m², not more than 5 mg/m², not morethan 4 mg/m², not more than 3 mg/m², not more than 2 mg/m², not morethan 1 mg/m², not more than 0.5 mg/m², not more than 0.1 mg/m², not morethan 0.05 mg/m², or not more than 0.01 mg/m².
 94. The release layer ofclaim 87, wherein the concentration of the chemical agent on the releaselayer is not more than 50 mg per square meter, not more than 40 mg/m²,not more than 30 mg/m², not more than 20 mg/m², not more than 10 mg/m²,not more than 5 mg/m², not more than 4 mg/m², not more than 3 mg/m², notmore than 2 mg/m², not more than 1 mg/m², not more than 0.5 mg/m², notmore than 0.1 mg/m², not more than 0.05 mg/m², or not more than 0.01mg/m².
 95. The release layer of claim 88, wherein the concentration ofthe chemical agent on the release layer is not more than 50 mg persquare meter, not more than 40 mg/m², not more than 30 mg/m², not morethan 20 mg/m², not more than 10 mg/m², not more than 5 mg/m², not morethan 4 mg/m², not more than 3 mg/m², not more than 2 mg/m², not morethan 1 mg/m², not more than 0.5 mg/m², not more than 0.1 mg/m², not morethan 0.05 mg/m², or not more than 0.01 mg/m².
 96. The release layer ofclaim 89, wherein the concentration of the chemical agent on the releaselayer is not more than 50 mg per square meter, not more than 40 mg/m²,not more than 30 mg/m², not more than 20 mg/m², not more than 10 mg/m²,not more than 5 mg/m², not more than 4 mg/m², not more than 3 mg/m², notmore than 2 mg/m², not more than 1 mg/m², not more than 0.5 mg/m², notmore than 0.1 mg/m², not more than 0.05 mg/m², or not more than 0.01mg/m².